This paper considers the fire resistance and failure modes of square hollow section (SHS) T-joints under axial compression at the brace end at elevated temperatures. Experimental tests on five full-scale joints with various geometries were performed. The specimens were first loaded with a constant load, resulting in a compressive reaction at the brace, then subjected to a heating process. The furnace heating followed a standard ISO 834 fire temperature curve. The specimens' temperature and deformations were measured until the specimens' failure. The results indicate that the final failure appears suddenly when the joint's temperature exceeds a critical value that is characteristic for each joint configuration. Three failure modes were observed, and the test results indicate that joint geometry affects the failure mode. A numerical study followed the experimental tests. A finite element model was created to simulate the behaviour of SHS T-joints under a brace's compression load. The model was validated and verified to obtain best representation of the joints' experimental behaviour.

In this paper, additive layer-by-layer fabrication of a fully screen printed monolithic supercapacitor exhibiting performance comparable with supercapacitors prepared using lamination is reported. A novel separator material improves the performance of the monolithic supercapacitor, is easily applicable using scalable processes such as screen and stencil printing, and is based on sustainable biomaterials. The additive monolithic manufacturing offers advantages for system integration and avoids the need of an additional alignment step as needed in the fabrication of laminated supercapacitors. Previously, the monolithically fabricated supercapacitors showed higher equivalent series resistance (ESR) and leakage current than the laminated ones. By using microfibrillated cellulose (MFC) and chitosan as separator materials ESR and leakage current were decreased. These disposable and non-toxic aqueous electrolyte supercapacitors are optimized for autonomous sensor systems, for example in Internet-of-Things (IoT) applications, with capacitance of 200–300 mF and ESR of about 10 Ω. The new composite separator material consisting of MFC and chitosan has good adhesion on the electrodes and the substrate, is easy to apply using printing and coating processes, and does not diffuse into the porous electrode. Graphic Abstract: [Figure not available: see fulltext.].

The effect of start-up on energy recovery and compositional changes in brewery wastewater in bioelectrochemical systems

Start-up of bioelectrochemical systems (BESs) fed with brewery wastewater was compared at different adjusted anode potentials (−200 and 0 mV vs. Ag/AgCl) and external resistances (50 and 1000 Ω). Current generation stabilized faster with the external resistances (9 ± 3 and 1.70 ± 0.04 A/m3 with 50 and 1000 Ω, respectively), whilst significantly higher current densities of 76 ± 39 and 44 ± 9 A/m3 were obtained with the adjusted anode potentials of −200 and 0 mV vs. Ag/AgCl, respectively. After start-up, when operated using 47 Ω external resistance, the current densities and Coulombic efficiencies of all BESs stabilized to 9.5 ± 2.9 A/m3 and 12 ± 2%, respectively, demonstrating that the start-up protocols were not critical for long-term BES operation in microbial fuel cell mode. With adjusted anode potentials, two times more biofilm biomass (measured as protein) was formed by the end of the experiment as compared to start-up with the fixed external resistances. After start-up, the organics in the brewery wastewater, mainly sugars and alcohols, were transformed to acetate (1360 ± 250 mg/L) and propionate (610 ± 190 mg/L). Optimized start-up is required for prompt BES recovery, for example, after process disturbances. Based on the results of this study, adjustment of anode potential to −200 mV vs. Ag/AgCl is recommended for fast BES start-up.

Current information on the links between the chemistry and hedonic liking of edible mushrooms is scarce. In this study, 84 consumers evaluated the appearance, odor, taste, texture and overall liking of samples of Nordic edible wild mushroom species. Subsequently, multivariate models on the effects of non-volatile compounds, odor-contributing volatile compounds, sensory attributes and hedonic likings were created. The non-volatile compounds were measured with quantitative NMR. The five studied mushroom species were different in their sugar and acid contents. Three consumer clusters were found with species*cluster interactions. Correlations with sensory attributes and chemical components were found, and the multivariate models indicated predictor attributes for each consumer cluster. The results indicate that the sensory properties could be correlated to both volatile and non-volatile compounds, there are consumer clusters with differing likings as regards mushrooms, and these clusters are heterogenic groups with no simple factors such as age explaining their liking scores.

Industrial chemical processes are struggling with adverse effects, such as corrosion and deposition, caused by gaseous alkali and heavy metal species. Mitigation of these problems requires novel monitoring concepts that provide information on gas-phase chemistry. However, selective optical online monitoring of the most problematic diatomic and triatomic species is challenging due to overlapping spectral features. In this work, a selective, all-optical, in situ gas-phase monitoring technique for triatomic molecules containing metallic atoms was developed and demonstrated with detection of PbCl2. Sequential collinear photofragmentation and atomic absorption spectroscopy (CPFAAS) enables determination of the triatomic PbCl2 concentration through detection of released Pb atoms after two consecutive photofragmentation processes. Absorption cross-sections of PbCl2, PbCl, and Pb were determined experimentally in a laboratory-scale reactor to enable calibration-free quantitative determination of the precursor molecule concentration in an arbitrary environment. Limit of detection for PbCl2 in the laboratory reactor was determined to be 0.25 ppm. Furthermore, the method was introduced for in situ monitoring of PbCl2 concentration in a 120 MWth power plant using demolition wood as its main fuel. In addition to industrial applications, the method can provide information on chemical reaction kinetics of the intermediate species that can be utilized in reaction simulations.

Extensive research over the past decades has identified integrins to be the primary transmembrane receptors that enable cells to respond to external mechanical cues. We reveal here a mechanism whereby syndecan-4 tunes cell mechanics in response to localized tension via a coordinated mechanochemical signalling response that involves activation of two other receptors: epidermal growth factor receptor and β1 integrin. Tension on syndecan-4 induces cell-wide activation of the kindlin-2/β1 integrin/RhoA axis in a PI3K-dependent manner. Furthermore, syndecan-4-mediated tension at the cell–extracellular matrix interface is required for yes-associated protein activation. Extracellular tension on syndecan-4 triggers a conformational change in the cytoplasmic domain, the variable region of which is indispensable for the mechanical adaptation to force, facilitating the assembly of a syndecan-4/α-actinin/F-actin molecular scaffold at the bead adhesion. This mechanotransduction pathway for syndecan-4 should have immediate implications for the broader field of mechanobiology.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Imperial College London, Queen Mary University of London, Fimlab Laboratories, University of Helsinki, Tampere University

Bibliographical note

Monitoring Charge Carrier Diffusion across a Perovskite Film with Transient Absorption Spectroscopy

We have developed a new noninvasive optical method for monitoring charge carrier diffusion and mobility in semiconductor thin films in the direction perpendicular to the surface which is most relevant for devices. The method is based on standard transient absorption measurements carried out in reflectance and transmittance modes at wavelengths below the band gap where the transient response is mainly determined by the change in refractive index, which in turn depends on the distribution of photogenerated carriers across the film. This distribution is initially inhomogeneous because of absorption at the excitation wavelength and becomes uniform over time via diffusion. By modeling these phenomena we can determine the diffusion constant and respective mobility. Applying the method to a 500 nm thick triple cation FAMACs perovskite film revealed that homogeneous carrier distribution is established in few hundred picoseconds, which is consistent with mobility of 66 cm2 (V s)-1.

Effect of tungsten and selenium on C1 gas bioconversion by an enriched anaerobic sludge and microbial community analysis

The effect of trace metals, namely tungsten and selenium, on the production of acids and alcohols through gas fermentation by a CO-enriched anaerobic sludge in a continuous gas-fed bioreactor was investigated. The CO-enriched sludge was first supplied with a tungsten-deficient medium (containing selenium) and in a next assay, a selenium-deficient medium (containing tungsten) was fed to the bioreactor, at a CO gas flow rate of 10 mL/min. In the absence of tungsten (tungstate), an initial pH of 6.2 followed by a pH decrease to 4.9 yielded 7.34 g/L acetic acid as the major acid during the high pH period. Subsequently, bioconversion of the acids at a lower pH of 4.9 yielded only 1.85 g/L ethanol and 1.2 g/L butanol in the absence of tungsten (tungstate). A similar follow up assay in the same bioreactor with two consecutive periods at different pH values (i.e., 6.2 and 4.9) with a selenium deficient medium yielded 6.6 g/L acetic acid at pH 6.2 and 4 g/L ethanol as well as 1.88 g/L butanol at pH 4.9. The results from the microbial community analysis showed that the only known CO fixing microorganism able to produce alcohols detected in the bioreactor was Clostridium autoethanogenum, both in the tungsten and the selenium deprived media, although that species has so far not been reported to be able to produce butanol. No other solventogenic acetogen was detected.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Materials Science and Environmental Engineering, Research group: Bio- and Circular Economy, University of La Coruña (UDC), UNESCO-IHE Institute for Water Education

Bibliographical note

Compounding and characterization of recycled multilayer plastic films

Mechanical recycling of multilayer plastic films from food packages was investigated. The multilayer films were manually separated from municipal solid waste, washed, grinded, and finally compounded at 0–100 wt% concentrations with virgin low-density polyethylene (PE-LD). Polyethylene grafted with maleic anhydride (PE-g-MA) compatibilizer was used in two of the compounds to replace 2 and 5 wt% of the PE-LD to study its effect as well. PE-g-MA is expected to improve the mechanical properties of the compounds by promoting the adhesion between incompatible polymer phases. The composition of the compounds was characterized with Fourier-transform infrared spectroscopy and differential scanning calorimetry and their properties were studied with tensile testing and rotational rheometer measurements. All tested compounds had relatively good mechanical properties and processability. This indicates that recycled multilayer films could replace at least part of the virgin PE-LD in applications where high-thermal stability or good visual appearance is not required. The PE-g-MA compatibilizer did not have a significant effect on the mechanical properties of the compounds.

Interactions between taste compounds and nanofibrillar cellulose were studied. For this, a new fluorescent indicator displacement method was developed. Two fluorescent indicators, namely, Calcofluor white and Congo red, were chosen because of their specific binding to cellulose and intrinsic fluorescence. Seven taste compounds with different structures were successfully measured together with nanofibrillar cellulose (NFC) and ranked according to their binding constants. The most pronounced interactions were found between quinine and NFC (1.4 × 104 M−1), whereas sucrose, aspartame and glutamic acid did not bind at all. Naringin showed moderate binding while stevioside and caffeine exhibited low binding. The comparison with microcrystalline cellulose indicates that the larger surface area of nanofibrillated cellulose enables stronger binding between the binder and macromolecules. The developed method can be further utilized to study interactions of different compound classes with nanocellulose materials in food, pharmaceutical and dye applications, using a conventional plate reader in a high-throughput manner.

Localized surface plasmon resonance has been investigated to enhance light harvesting in hematite-based photoelectrodes modified with gold nanoparticles (AuNPs); meanwhile, an extensive understanding about the different processes involved in the hematite-AuNP system remains unclear. This work addresses a majority of effects associated with AuNP addition by comparing charge transfer, catalytic and light harvesting efficiencies. The obtained results revealed that the lower AuNP amount leads to a higher photocurrent response of 1.20 mA cm-2 at 1.23 VRHE in comparison with all photoelectrodes designed here. X-ray photoelectron data revealed that hematite photoelectrodes loaded with higher concentrations of AuNPs immersed in an alkaline electrolyte showed hydrated/oxidized gold phase formation at the electrode/electrolyte interface. This change on the semiconductor-metal interface may affect the conductivity impairing the photocatalytic performance because of the passivation layer on the AuNP surface, decreasing the efficiency of charge transfer. Notoriously, increasing AuNP amount supported on the hematite surface clearly promoted higher light absorption, which was surprisingly not followed by photoelectrochemical efficiency. This result suggests here that the plasmon effect is not a dominant phenomenon that drives the photoelectrode performance. In fact, a deeper analysis showed that the loaded hematite photoelectrodes with low amounts of AuNPs provides a Schottky contact at the semiconductor-metal interface leading to Fermi level equilibration enhancing charge transport efficiency, which is classified as the predominant effect leading to higher photoresponse in the system.

This paper presents a systematic study of the effect of various WC-CoCr powders on the residual stresses of the high pressure HVOF sprayed coating. As the residual stresses are recognized to play a significant role in the mechanical and fatigue resistance of the coating, it is understandable that their management is important for damage tolerant coating design. Several studies have recently shown that processes, which produce high particle kinetic energy and lower particle temperature, such as Warm spray, HVAF and high-pressure HVOF processes, generate higher peening stresses and therefore final residual stresses is more compressive compared to lower kinetic energy HVOF systems. In addition to the spraying process, powder properties are known to be one of the most important variables in thermal spraying. Nevertheless, only few studies can be found on the effect of powder properties on residual stresses. The aim of this study was to understand the effect of different powder properties on the formation of residual stress. In situ monitoring was utilized to record curvature and temperature during spraying and to calculate coating residual stresses. This approach is a useful tool for understanding of residual stresses during the thermal spraying process enabling their manipulation. It was found that the powders, with only minor differences in density and particle size, produced a significant difference of about 350 MPa in the stress states of the coatings. The combined effect of spray powder properties and spray parameters on residual stress was almost 560 MPa.

Non-radiative decay and fragmentation in water molecules after 1 a 1-1 4 a 1 excitation and core ionization studied by electron-energy-resolved electron-ion coincidence spectroscopy

In this paper, we examine decay and fragmentation of core-excited and core-ionized water molecules combining quantum chemical calculations and electron-energy-resolved electron-ion coincidence spectroscopy. The experimental technique allows us to connect electronic decay from core-excited states, electronic transitions between ionic states, and dissociation of the molecular ion. To this end, we calculate the minimum energy dissociation path of the core-excited molecule and the potential energy surfaces of the molecular ion. Our measurements highlight the role of ultra-fast nuclear motion in the 1a1-14a1 core-excited molecule in the production of fragment ions. OH+ fragments dominate for spectator Auger decay. Complete atomization after sequential fragmentation is also evident through detection of slow H+ fragments. Additional measurements of the non-resonant Auger decay of the core-ionized molecule (1a1-1) to the lower-energy dication states show that the formation of the OH+ + H+ ion pair dominates, whereas sequential fragmentation OH+ + H+ → O + H+ + H+ is observed for transitions to higher dication states, supporting previous theoretical investigations.

Comparison and impact of different fiber debond techniques on fiber reinforced flexible composites

The focus of this paper is the realization and verification of a modified fiber bundle pull-out test setup to estimate the adhesion properties between threads and elastic matrix materials with a more realistic failure mode than single fiber debond techniques. This testing device including a modified specimen holder provides the basis for an adequate estimation of the interlaminar adhesion of fiber bundles including the opportunity of a faster, easier, and more economic handling compared to single fiber tests. The verification was done with the single-fiber and microbond test. Overall, the modified test setup showed the typical pull-out behavior, and the relative comparability between different test scales is given.

High-resolution analysis of the ν3 band of radiocarbon methane 14CH4

We present the first high-resolution measurements and rotational analysis of the fundamental asymmetric stretching vibrational band ν3(F2) of radiocarbon methane. A spectrometer consisting of a mid-infrared continuous-wave optical parametric oscillator and a cantilever-enhanced photoacoustic detector was employed to determine the wavenumbers of 43 rovibrational lines. A spectroscopic model could reproduce all the observed transition wavenumbers within the accuracy of the experiment. Our work contributes to the development of radiocarbon methane detectors based on laser spectroscopy.

Almost inevitable climate change and increasing pollution levels around the world are the most significant drivers for the environmental monitoring evolution. Recent activities in the field of wireless sensor networks have made tremendous progress concerning conventional centralized sensor networks known for decades. However, most systems developed today still face challenges while estimating the trade-off between their flexibility and security. In this work, we provide an overview of the environmental monitoring strategies and applications. We conclude that wireless sensor networks of tomorrow would mostly have a distributed nature. Furthermore, we present the results of the developed secure distributed monitoring framework from both hardware and software perspectives. The developed mechanisms provide an ability for sensors to communicate in both infrastructure and mesh modes. The system allows each sensor node to act as a relay, which increases the system failure resistance and improves the scalability. Moreover, we employ an authentication mechanism to ensure the transparent migration of the nodes between different network segments while maintaining a high level of system security. Finally, we report on the real-life deployment results.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Electrical Engineering, Research group: Emerging Technologies for Nano-Bio-Info-Cogno, St. Petersburg State University of Aerospace Instrumentation, ITMO University, Brno University of Technology, National Research University Higher School of Economics

Living systems have inspired research on non-biological dynamic materials and systems chemistry to mimic specific complex biological functions. Upon pursuing ever more complex life-inspired non-biological systems, mimicking even the most elementary aspects of learning is a grand challenge. We demonstrate a programmable hydrogel-based model system, whose behaviour is inspired by associative learning, i.e., conditioning, which is among the simplest forms of learning. Algorithmically, associative learning minimally requires responsivity to two different stimuli and a memory element. Herein, nanoparticles form the memory element, where a photoacid-driven pH-change leads to their chain-like assembly with a modified spectral behaviour. On associating selected light irradiation with heating, the gel starts to melt upon the irradiation, originally a neutral stimulus. A logic diagram describes such an evolution of the material response. Coupled chemical reactions drive the system out-of-equilibrium, allowing forgetting and memory recovery. The findings encourage to search non-biological materials towards associative and dynamic properties.

Key drivers of cloud response to surface-active organics

Aerosol-cloud interactions constitute the largest source of uncertainty in global radiative forcing estimates, hampering our understanding of climate evolution. Recent empirical evidence suggests surface tension depression by organic aerosol to significantly influence the formation of cloud droplets, and hence cloud optical properties. In climate models, however, surface tension of water is generally assumed when predicting cloud droplet concentrations. Here we show that the sensitivity of cloud microphysics, optical properties and shortwave radiative effects to the surface phase are dictated by an interplay between the aerosol particle size distribution, composition, water availability and atmospheric dynamics. We demonstrate that accounting for the surface phase becomes essential in clean environments in which ultrafine particle sources are present. Through detailed sensitivity analysis, quantitative constraints on the key drivers – aerosol particle number concentrations, organic fraction and fixed updraft velocity – are derived for instances of significant cloud microphysical susceptibilities to the surface phase.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Stockholm University, University of Exeter, University of California, Riverside, Lawrence Berkeley National Laboratory, University of Manchester

Bibliographical note

The role of highly oxygenated organic molecules in the Boreal aerosol-cloud-climate system

Over Boreal regions, monoterpenes emitted from the forest are the main precursors for secondary organic aerosol (SOA) formation and the primary driver of the growth of new aerosol particles to climatically important cloud condensation nuclei (CCN). Autoxidation of monoterpenes leads to rapid formation of Highly Oxygenated organic Molecules (HOM). We have developed the first model with near-explicit representation of atmospheric new particle formation (NPF) and HOM formation. The model can reproduce the observed NPF, HOM gas-phase composition and SOA formation over the Boreal forest. During the spring, HOM SOA formation increases the CCN concentration by ~10 % and causes a direct aerosol radiative forcing of −0.10 W/m2. In contrast, NPF reduces the number of CCN at updraft velocities < 0.2 m/s, and causes a direct aerosol radiative forcing of +0.15 W/m2. Hence, while HOM SOA contributes to climate cooling, NPF can result in climate warming over the Boreal forest.

In this paper, we have applied a recently developed complex-domain hyperspectral denoiser for the object recognition task, which is performed by the correlation analysis of investigated objects’ spectra with the fingerprint spectra from the same object. Extensive experiments carried out on noisy data from digital hyperspectral holography demonstrate a significant enhancement of the recognition accuracy of signals masked by noise, when the advanced noise suppression is applied.

Nanocluster Aerosol Emissions of a 3D Printer

Many studies exist that characterize the aerosol emissions from fused filament fabrication three-dimensional (3D) printers. However, nanocluster aerosol (NCA) particles, that is particles in a size range under 3 nm, are rarely studied. The purpose of this study was to characterize the NCA emissions and the contribution of NCA to the total particle number emissions from a 3D printer. We used a particle size magnifier and a scanning mobility particle sizer to measure the time evolution of particle size distribution, which was used to calculate the average NCA emission rates during a printer operation in a chamber. The NCA emission rates ranged from 1.4 × 106 to 7.3 × 109 s-1 depending on the applied combination of filament material and nozzle temperature, showing increasing emission with increasing temperature. The NCA emissions constitute from 9 to 48% of the total emissions, that is, almost half of the particle emissions may have been previously neglected. Therefore, it is essential to include the low NCA size range in, for example, future 3D-printer-testing protocols, emission measurement standards, and risk management measures.

Bibliographical note

Molecular Composition and Volatility of Nucleated Particles from α-Pinene Oxidation between -50 °c and +25 °c

We use a real-time temperature-programmed desorption chemical-ionization mass spectrometer (FIGAERO-CIMS) to measure particle-phase composition and volatility of nucleated particles, studying pure α-pinene oxidation over a wide temperature range (-50 °C to +25 °C) in the CLOUD chamber at CERN. Highly oxygenated organic molecules are much more abundant in particles formed at higher temperatures, shifting the compounds toward higher O/C and lower intrinsic (300 K) volatility. We find that pure biogenic nucleation and growth depends only weakly on temperature. This is because the positive temperature dependence of degree of oxidation (and polarity) and the negative temperature dependence of volatility counteract each other. Unlike prior work that relied on estimated volatility, we directly measure volatility via calibrated temperature-programmed desorption. Our particle-phase measurements are consistent with gas-phase results and indicate that during new-particle formation from α-pinene oxidation, gas-phase chemistry directly determines the properties of materials in the condensed phase. We now have consistency between measured gas-phase product concentrations, product volatility, measured and modeled growth rates, and the particle composition over most temperatures found in the troposphere.

Barkhausen noise testing (BNT) is a nondestructive method for investigating many properties of ferromagnetic materials. The most common application is the monitoring of grinding burns caused by introducing locally high temperatures while grinding. Other features, such as microstructure, residual stress changes, hardening depth, and so forth, can be monitored as well. Nevertheless, because BNT is a method based on a complex magnetoelectric phenomenon, it is not yet standardized. Therefore, there is a need to study the traceability and stability of the measurement method. This study aimed to carry out a statistical analysis of ferromagnetic samples after grinding processes by the use of BNT. The first part of the experiment was to grind samples in different facilities (Sweden and Finland) with similar grinding parameters, different grinding wheels, and different hardness values. The second part was to evaluate measured BNT parameters to determine significant factors affecting BNT signal value. The measurement data from the samples were divided into two different batches according to where they were manufactured. Both grinding batches contained measurement data from three different participants. The main feature for calculation was the root-mean-square (RMS) value. The first processing step was to normalize the RMS values for all the measurements. A standard analysis of variance (ANOVA) was applied for the normalized dataset. The ANOVA showed that the grinding parameters had a significant impact on the BNT signal value, while the other investigated factors (e.g., participant) were negligible. The reasons for this are discussed at the end of the paper.

Controlled Orientations of Neighboring Tetracene Units by Mixed Self-Assembled Monolayers on Gold Nanoclusters for High-Yield and Long-Lived Triplet Excited States through Singlet Fission

Although tetracene (Tc) is well-known as a good candidate for singlet fission (SF), the number of high-yield and long-lived triplet excited states through SF is extremely limited because of the relative acceleration of the reverse triplet-triplet annihilation (TTA) considering the energy matching between a singlet and two triplet states. Systematic control of electronic interactions between two neighboring units using conventional covalent linkages and molecular assembly methods to optimize these kinetic processes is quite difficult because of the complicated synthesis and random orientations. In this study, we propose a novel supramolecular strategy utilizing mixed self-assembled monolayers (SAMs) with two different chain lengths. Specifically, mixed Tc-SAMs on gold nanoclusters, which are prepared using Tc-modified heterodisulfides with two different chain lengths, attain high-yield SF (ΦSF ≈ 90%) and individual triplet yields (ΦΤ ≈ 160%). The obtained ΦSF is the highest value among Tc derivatives in homogeneous solution to the best of our knowledge.

Effects of anode materials on electricity production from xylose and treatability of TMP wastewater in an up-flow microbial fuel cell

The aim of this study was to determine an optimal anode material for electricity production and COD removal from xylose containing synthetic wastewater in an up-flow microbial fuel cell (MFC), and assess its suitability for treatment of thermomechanical pulping (TMP) wastewater with an enrichment culture at 37 °C. The anode materials tested included carbon-based electrodes (graphite plate, carbon cloth and zeolite coated carbon cloth), metal-based electrodes (tin coated copper) and a metal-carbon assembly (granular activated carbon in stainless steel cage). During continuous operation with xylose, COD removal was 77–86% of which 25–28% was recovered as electricity. The highest power density of 333 (±15) mW/m
2
was obtained with the carbon cloth electrode. However, based on an overall analysis including electrode performance, surface area and scalability, the granular activated carbon in stainless steel cage (GAC in SS cage) was chosen to be used as electrode for bioelectrochemical treatment of TMP wastewater. The TMP fed MFC was operated in continuous mode with 1.8 days hydraulic retention time, resulting in 47 (±13%) COD removal of which 1.5% was recovered as electricity with the average power production of 10–15 mW/m
2
. During operation with TMP wastewater, membrane fouling increased the polarization resistance causing a 50% decrease in power production within 30 days. This study shows that MFC pretreatment removes half of the TMP wastewater COD load, reducing the energy required for aerobic treatment.

Multiresonant High-Q Plasmonic Metasurfaces

Resonant metasurfaces are devices composed of nanostructured subwavelength scatterers that generate narrow optical resonances, enabling applications in filtering, nonlinear optics, and molecular fingerprinting. It is highly desirable for these applications to incorporate such devices with multiple high-quality-factor resonances; however, it can be challenging to obtain more than a pair of narrow resonances in a single plasmonic surface. Here, we demonstrate a multiresonant metasurface that operates by extending the functionality of surface lattice resonances, which are the collective responses of arrays of metallic nanoparticles. This device features a series of resonances with high-quality factors (Q ∼ 40), an order of magnitude larger than what is typically achievable with plasmonic nanoparticles, as well as a narrow free spectral range. This design methodology can be used to better tailor the transmission spectrum of resonant metasurfaces and represents an important step toward the miniaturization of optical devices.

Strategies To Diminish the Emissions of Particles and Secondary Aerosol Formation from Diesel Engines

Particle emissions and secondary aerosol formation from internal combustion engines deteriorate air quality and significantly affect human wellbeing and health. Both the direct particle emissions and the emissions of compounds contributing to secondary aerosol formation depend on choices made in selecting fuels, engine technologies, and exhaust aftertreatment (EAT). Here we study how catalytic EATs, particle filtration, and fuel choices affect these emissions concerning heavy-duty diesel engine. We observed that the most advanced EAT decreased the emissions of fresh exhaust particle mass as much as 98% (from 44.7 to 0.73 mg/kWh) and the formation of aged exhaust particle mass ∼100% (from 106.2 to ∼0 mg/kWh). The composition of emitted particles depended significantly on the EAT and oxidative aging. While black carbon typically dominated the composition of fresh exhaust particles, aged particles contained more sulfates and organics. The fuel choices had minor effects on the secondary aerosol formation, implicating that, in diesel engines, either the lubricant is a significant source of secondary aerosol precursors or the precursors are formed in the combustion process. Results indicate that the utilization of EAT in diesel engines would produce benefits with respect to exhaust burden on air quality, and thus their utilization should be promoted especially in geographical areas suffering from poor air quality.

In the last decade, several studies have shown that polybutylene succinate (PBSu)has a high potential as a biomaterial enabling cell adhesion and growth. In this study, porous PBSu films have been prepared by the breath figure method (BF)and by particulate leaching (PL), and characterized in terms of thickness, surface properties, diffusion capacity and in vitro stability. Because porous films are of high interest for tissue engineering of retinal pigment epithelium (RPE), the initial viability and adhesion of human embryonic stem cell-derived RPE onto the PBSu films was then evaluated. To the best of our knowledge, this is the first study on the adhesion behavior of hESC-RPE onto porous and biodegradable polymer surfaces. The results clearly demonstrated that the two manufacturing methods produced materials with very distinct properties. Films produced by BF expressively demonstrated the highest roughness and surface area, and the lowest water contact angle. These features likely contributed to increase the biocompatibility of the surface, particularly when coated with laminin and collagen IV, as observed by the improved cell viability, cell morphology, adhesion and production of extracellular matrix proteins. Altogether, our results showed not only that PBSu holds high potential in retinal tissue engineering, but also that the physical properties and biocompatibility of the material are highly dependent on the adopted casting method.

Behavior of the DPH fluorescence probe in membranes perturbed by drugs

1,6-Diphenyl-1,3,5-hexatriene (DPH) is one of the most commonly used fluorescent probes to study dynamical and structural properties of lipid bilayers and cellular membranes via measuring steady-state or time-resolved fluorescence anisotropy. In this study, we present a limitation in the use of DPH to predict the order of lipid acyl chains when the lipid bilayer is doped with itraconazole (ITZ), an antifungal drug. Our steady-state fluorescence anisotropy measurements showed a significant decrease in fluorescence anisotropy of DPH embedded in the ITZ-containing membrane, suggesting a substantial increase in membrane fluidity, which indirectly indicates a decrease in the order of the hydrocarbon chains. This result or its interpretation is in disagreement with the fluorescence recovery after photobleaching measurements and molecular dynamics (MD) simulation data. The results of these experiments and calculations indicate an increase in the hydrocarbon chain order. The MD simulations of the bilayer containing both ITZ and DPH provide explanations for these observations. Apparently, in the presence of the drug, the DPH molecules are pushed deeper into the hydrophobic membrane core below the lipid double bonds, and the probe predominately adopts the orientation of the ITZ molecules that is parallel to the membrane surface, instead of orienting parallel to the lipid acyl chains. For this reason, DPH anisotropy provides information related to the less ordered central region of the membrane rather than reporting the properties of the upper segments of the lipid acyl chains.

Dynamic covalent chemistry forming hydrazone and oxime linkages is attractive due to its simplicity, selectivity and compatibility under aqueous conditions. However, the low reaction rate at physiological pH hampers its use in biomedical applications. Herein, we present different monovalent and bivalent aqueous salt solutions as bio-friendly, non-toxic catalysts which can drive the hydrazone and oxime reactions with excellent efficacy at physiological pH. Direct comparison of hydrazone and oxime reactions using a small molecule model, without any salt catalysis, indicated that oxime formation is 6-times faster than hydrazone formation. Addition of different salts (NaCl, NaBr, KCl, LiCl, LiClO4, Na2SO4, MgCl2 and CaCl2) accelerated the pseudo-first-order reaction kinetics by ∼1.2-4.9-fold for acylhydrazone formation and by ∼1.5-6.9-fold for oxime formation, in a concentration-dependent manner. We further explored the potential of such catalysts to develop acylhydrazone and oxime cross-linked hyaluronic acid (HA) hydrogels with different physicochemical properties without changing the degree of chemical modification. Analogous to the small molecule model system, the addition of monovalent and divalent salts as catalysts significantly reduced the gelling time. The gelling time for the acylhydrazone cross-linked HA-hydrogel (1.6 wt%) could be reduced from 300 min to 1.2 min by adding 100 mM CaCl2, while that for the oxime cross-linked HA-hydrogel (1.2 wt%) could be reduced from 68 min to 1.1 min by adding 50 mM CaCl2. This difference in the gelling time also resulted in hydrogels with differential swelling properties as measured after 24 h. Our results are the first to demonstrate the use of salts, for catalyzing hydrogel formation under physiologically relevant conditions.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: BioMediTech, Research group: Biomaterials and Tissue Engineering Group, University of Montreal, Uppsala University

The fatigue life of thermally sprayed Al2O3- and Cr2O3-based coatings has been studied under low-energy (0.7–5 mJ) impact conditions. A threshold impact energy and amount of repetitions the coatings can endure with said energy before catastrophic failure was obtained. The catastrophic failure was determined to occur when the fracture mode of the coating switched from brittle cone cracking to quasi-plastic radial cracking. The results are examined relative to the microstructural features along with other properties of the coatings - hardness and cavitation resistance. The experiment provided a new approach for a straightforward comparison of the micro-scale impact fatigue life of thermally sprayed coatings unachievable with previous methods.

A novel method that combines thermal analysis and traditional furnace corrosion tests was used to study the corrosion behaviour of thermally sprayed Cr3C2-based hardmetal coatings at 450 °C and 550 °C under a KCl deposit. This method enabled the identification of the onset temperature of chlorine-induced oxidation to be within 450–500 °C. Two corrosion mechanisms were suggested for these temperatures. At 450 °C, the corrosion rate was slow and mainly controlled by the formation of K2CrO4. Exposure at 550 °C caused the formation of fine interconnected secondary-carbide precipitates in the metal matrix. Their fast corrosion was identified as the major cause of degradation.

The inversion of reflectance models is a generalizable tool to obtain estimates on forest biophysical parameters, such as leaf area index, with theoretically little information need from a study area, instead relying on the knowledge about physical processes in the forest radiation regime. The use of prior information can greatly improve the reflectance model inversion, however, the literature does not yet provide much information on the selection of priors and their influence on the inversion results. In this study, we used a Bayesian approach to invert the PARAS forest reflectance model and retrieve leaf area index from Sentinel-2 MSI and Landsat 8 OLI multispectral satellite images. The PARAS model is based on the theory of spectral invariants, which describes the influence of wavelength-independent parameters on forest radiative transfer. The Bayesian inversion approach is highly flexible, provides uncertainty quantification, and enables the explicit incorporation of prior knowledge into the inversion process. We found that the choice of prior information is crucial in inverting a forest reflectance model to predict leaf area index. Regularizing and informative priors for leaf area index strongly improved the predictions, relative to an uninformative prior, in that they counteracted the saturation effect of the optical signal occuring at high values for leaf area index. The predictions of leaf area index were more accurate for Landsat 8 than for Sentinel-2, due to potential inconsistencies in the visible bands of Sentinel-2 in our data, and the higher spectral resolution.

Photochemistry of dithiophosphinate Ni(S2P(i-Bu)2)2 complex in CCl4. Transient species and TD-DFT calculations

Femtosecond spectroscopy and nanosecond laser flash photolysis were used to study the photophysical and photochemical transformations of the bis-diisobutyl-dithiophosphinate Ni(II)complex (Ni(S2P(i-Bu)2)2 = Ni(dtpi)2, where dtpi− ≡ −S2P(i-Bu)2)in CCl4 solutions. The radiation of second harmonic (405 nm)of Ti:Sapphire laser transfers the Ni(dtpi)2 complex to an excited 1LMCT state. Its decay in CCl4 is described by three exponents with time constants 0.58, 2.0 and ˜150 ps. The first process apparently involves the fast transitions from 1LMCT state to 3LMCT due to the intersystem crossing (ISC)and then to lower-lying “hot” 3LF (Ligand Field)state. The second time constant, most likely, corresponds to the vibrational cooling of this “hot” 3LF state. And the third slow process is the transition from 3LF state to ground state (1GS). The quantum yield of photochemical transformation under the 405 irradiation is close to zero, so the study of photochemistry was performed with a nanosecond flash photolysis at 308 nm. In this case an electron transfer from the excited Ni(dtpi)2 complex to a solvent molecule leads to the appearance of primary intermediate, the [ClNi(dtpi)(dtpi[rad])]complex, in which a dtpi[rad] radical is coordinated with a nickel ion via one sulfur atom. In the fast reaction with Ni(dtpi)2, this complex forms a long-lived dimer ClNi(dtpi)(dtpi[rad])[Ni(dtpi)2]. This intermediate for a few hundred microseconds decays in the reaction of recombination with the formation of (dtpi)2 disulphide and unstable ClNi(dtpi)complex. The insoluble NiCl2 salt falled in CCl4 as the sediment due to the reaction of two ClNi(dtpi)complexes. The quantum chemical calculations allowed to determine the geometry of the intermediate complexes arising in the photochemistry of Ni(S2P(i-Bu)2)2 complex.

Bibliographical note

Observation of Coexistence of Yu-Shiba-Rusinov States and Spin-Flip Excitations

We investigate the spectral evolution in different metal phthalocyanine molecules on NbSe2 surface using scanning tunnelling microscopy (STM) as a function of the coupling with the substrate. For manganese phthalocyanine (MnPc), we demonstrate a smooth spectral crossover from Yu-Shiba-Rusinov (YSR) bound states to spin-flip excitations. This has not been observed previously and it is in contrast to simple theoretical expectations. We corroborate the experimental findings using numerical renormalization group calculations. Our results provide fundamental new insight on the behavior of atomic scale magnetic/SC hybrid systems, which is important, for example, for engineered topological superconductors and spin logic devices.

In response to the 2013 Update of the European Strategy for Particle Physics (EPPSU), the Future Circular Collider (FCC) study was launched as a world-wide international collaboration hosted by CERN. The FCC study covered an energy-frontier hadron collider (FCC-hh), a highest-luminosity high-energy lepton collider (FCC-ee), the corresponding 100 km tunnel infrastructure, as well as the physics opportunities of these two colliders, and a high-energy LHC, based on FCC-hh technology. This document constitutes the third volume of the FCC Conceptual Design Report, devoted to the hadron collider FCC-hh. It summarizes the FCC-hh physics discovery opportunities, presents the FCC-hh accelerator design, performance reach, and staged operation plan, discusses the underlying technologies, the civil engineering and technical infrastructure, and also sketches a possible implementation. Combining ingredients from the Large Hadron Collider (LHC), the high-luminosity LHC upgrade and adding novel technologies and approaches, the FCC-hh design aims at significantly extending the energy frontier to 100 TeV. Its unprecedented centre of-mass collision energy will make the FCC-hh a unique instrument to explore physics beyond the Standard Model, offering great direct sensitivity to new physics and discoveries.

Pyrolytic behavior of lignocellulosic-based polysaccharides

The thermochemical behavior of cellulose, glucomannan, and xylan was investigated by pyrolysis–gas chromatography-mass spectrometry (Py-GC/MS). In each case, major GC-amenable condensable products were classified into several compound groups, and the formation of these monomer-related fragments from the model substance samples was determined at 500, 600, and 700 °C with a residence time of 5 s and 20 s. The results revealed that despite some general formation trends, no compound group was selectively formed at certain temperatures. Of the 11 product groups, the primary ones, including lactone, furan, and cyclopentenone derivatives, accounted for 72–85% (from cellulose), 86–90% (from glucomannan), and 76–81% (from xylan) of the total amount of pyrolysis products determined. At 500 °C, about half of the major product groups accounted for lactones, such as 3-hydroxy-2-penteno-1,5-lactone and 5H-furan-2-one. It was also confirmed by thermogravimetric analyses that within the temperature range studied, cellulose was thermally more stable than the heterogeneous hemicelluloses. These kinds of data are of importance, for example, with respect to efforts to develop new biorefinery possibilities for renewable resources.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Research group: Bio- and Circular Economy, University of Jyvaskyla

Dry eye syndrome (DES), one of the most common ophthalmological diseases, is typically caused by excessive evaporation of tear fluid from the ocular surface. Excessive evaporation is linked to impaired function of the tear film lipid layer (TFLL) that covers the aqueous tear film. The principles of the evaporation resistance of the TFLL have remained unknown, however. We combined atomistic simulations with Brewster angle microscopy and surface potential experiments to explore the organization and evaporation resistance of films composed of wax esters, one of the main components of the TFLL. The results provide evidence that the evaporation resistance of the TFLL is based on crystalline-state layers of wax esters and that the evaporation rate is determined by defects in the TFLL and its coverage on the ocular surface. On the basis of the results, uncovering the nonequilibrium spreading and crystallization of TFLL films has potential to reveal new means of treating DES.

A new biomimetic stimuli-responsive adaptive elastomeric material, whose mechanical properties are altered by a water treatment is reported in this paper. This material is a calcium sulphate (CaSO4) filled composite with an epoxidized natural rubber (ENR) matrix. By exploiting various phase transformation processes that arise when CaSO4 is hydrated, several different crystal structures of CaSO4·xH2O can be developed in the cross-linked ENR matrix. Significant improvements in the mechanical and thermal properties are then observed in the water-treated composites. When compared with the untreated sample, there is approximately 100% increase in the dynamic modulus. The thermal stability of the composites is also improved by increasing the maximum degradation rate temperature by about 20 °C. This change in behavior results from an in situ development of hydrated crystal structures of the nanosized CaSO4 particles in the ENR matrix, which has been verified using Raman spectroscopy, transmission electron microscopy, atomic force microscopy, and X-ray scattering. This work provides a promising and relatively simple pathway for the development of next generation of mechanically adaptive elastomeric materials by an eco-friendly route, which may eventually also be developed into an innovative biodegradable and biocompatible smart polymeric material.

Epitaxial phases of high Bi content GaSbBi alloys

GaSbBi alloys have recently emerged as attractive materials for mid-infrared optoelectronics owing to strong band gap reduction enabled by Bi incorporation into the GaSb matrix. The fundamental understanding of the epitaxial process required to demonstrate high quality crystals is in an early-developmental phase. From this perspective, we report on the key role played by the Sb/Ga flux ratio in controlling the structural quality and incorporation of high Bi content GaSbBi (up to 14.5%-Bi), revealing three distinct epitaxial phases. The first phase (below stoichiometric Sb/Ga) exhibits Ga-Bi compound droplets, low crystal quality, and reduced Bi content. At the second phase (above stoichiometric Sb/Ga), the crystal exhibits smooth surfaces and excellent crystallinity with efficient Bi incorporation. The last phase corresponds to exceeding a Sb/Ga threshold that leads to reduced Bi incorporation, Bi droplets and degraded crystallinity. This threshold value that defines the optimal growth window is controlled by the temperature as well as the Bi/Ga ratio. Increasing temperature increases the threshold, albeit simultaneously reducing Bi incorporation. Conversely, increasing the Bi/Ga flux ratio increases Bi incorporation, while narrowing down and ultimately closing the window. This study provides a general framework enabling development of high quality GaSbBi heterostructures for emerging mid-infrared optoelectronics.

Tailoring Second-Harmonic Emission from (111)-GaAs Nanoantennas

Second-harmonic generation (SHG) in resonant dielectric Mie-scattering nanoparticles has been hailed as a powerful platform for nonlinear light sources. While bulk-SHG is suppressed in elemental semiconductors, for example, silicon and germanium due to their centrosymmetry, the group of zincblende III-V compound semiconductors, especially (100)-grown AlGaAs and GaAs, have recently been presented as promising alternatives. However, major obstacles to push the technology toward practical applications are the limited control over directionality of the SH emission and especially zero forward/backward radiation, resulting from the peculiar nature of the second-order nonlinear susceptibility of this otherwise highly promising group of semiconductors. Furthermore, the generated SH signal for (100)-GaAs nanoparticles depends strongly on the polarization of the pump. In this work, we provide both theoretically and experimentally a solution to these problems by presenting the first SHG nanoantennas made from (111)-GaAs embedded in a low index material. These nanoantennas show superior forward directionality compared to their (100)-counterparts. Most importantly, based on the special symmetry of the crystalline structure, it is possible to manipulate the SHG radiation pattern of the nanoantennas by changing the pump polarization without affecting the linear properties and the total nonlinear conversion efficiency, hence paving the way for efficient and flexible nonlinear beam-shaping devices.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Research group: Nonlinear Optics, Physics, Australian National University, Friedrich-Schiller-University Jena, School of Engineering and Information Technology, University of New South Wales (UNSW) Australia, Russian Academy of Sciences

The Role of Temperature and Lipid Charge on Intake/Uptake of Cationic Gold Nanoparticles into Lipid Bilayers

Understanding the molecular mechanisms governing nanoparticle–membrane interactions is of prime importance for drug delivery and biomedical applications. Neutron reflectometry (NR) experiments are combined with atomistic and coarse-grained molecular dynamics (MD) simulations to study the interaction between cationic gold nanoparticles (AuNPs) and model lipid membranes composed of a mixture of zwitterionic di-stearoyl-phosphatidylcholine (DSPC) and anionic di-stearoyl-phosphatidylglycerol (DSPG). MD simulations show that the interaction between AuNPs and a pure DSPC lipid bilayer is modulated by a free energy barrier. This can be overcome by increasing temperature, which promotes an irreversible AuNP incorporation into the lipid bilayer. NR experiments confirm the encapsulation of the AuNPs within the lipid bilayer at temperatures around 55 °C. In contrast, the AuNP adsorption is weak and impaired by heating for a DSPC–DSPG (3:1) lipid bilayer. These results demonstrate that both the lipid charge and the temperature play pivotal roles in AuNP–membrane interactions. Furthermore, NR experiments indicate that the (negative) DSPG lipids are associated with lipid extraction upon AuNP adsorption, which is confirmed by coarse-grained MD simulations as a lipid-crawling effect driving further AuNP aggregation. Overall, the obtained detailed molecular view of the interaction mechanisms sheds light on AuNP incorporation and membrane destabilization.

When a force probe with a small liquid drop adhered to its tip makes contact with a substrate of interest, the normal force right after contact is called the snap-in force. This snap-in force is related to the advancing contact angle or the contact radius at the substrate. Measuring snap-in forces has been proposed as an alternative to measure the advancing contact angles of surfaces. The snap-in occurs when the distance between the probe surface and the substrate is hS, which is amenable to geometry, assuming the drop was a spherical cap before snap-in. Equilibrium is reached at a distance hE < hS. At equilibrium, the normal force F = 0, and the capillary bridge is a spherical segment, amenable again to geometry. For a small normal displacement Δh = h - hE, the normal force can be approximated with F ≈ -k1Δh or F ≈ -k1Δh - k2Δh2, where k1 = -∂F/∂h and k2 = -1/2·∂2F/∂h2 are the effective linear and quadratic spring constants of the bridge, respectively. Analytical expressions for k1,2 are found using Kenmotsu's parameterization. Fixed contact angle and fixed contact radius conditions give different forms of k1,2. The expressions for k1 found here are simpler, yet equivalent to the earlier derivation by Kusumaatmaja and Lipowsky (2010). Approximate snap-in forces are obtained by setting Δh = hS - hE. These approximate analytical snap-in forces agree with the experimental data from Liimatainen et al. (2017) and a numerical method based on solving the shape of the interface. In particular, the approximations are most accurate for super liquid-repellent surfaces. For such surfaces, readers may find this new analytical method more convenient than solving the shape of the interface numerically.

A better understanding of cellulose-cellulose interactions is needed in applications such as paper making and all-cellulose composites. To date, cellulose-cellulose studies have been chemistry-oriented. In these studies, the sample surfaces have been modified with different chemicals and then tested under an atomic force microscope (AFM) using a colloidal probe (CP). Studies of cellulose-cellulose interaction based on sample morphology and mechanical properties have been rare as a result of the complex surface structure and the soft texture of the cellulose. The current surface interaction models, such as the Johnson-Kendall-Roberts (JKR) model in which the studied bodies are assumed to have smooth surfaces, can no longer fully reveal the interfacial behavior between two cellulose surfaces. Therefore, we propose a new type of contact model for rough-rough interaction by dividing the surface contacts into primary and secondary levels. The main idea of the new model is to take into account local individual contact details between rough surfaces. The model considers the effect of the surface topography by including the asperities and valleys on a cellulose sphere used as the colloidal probe in imaging the topography of a cellulose membrane (CM). In addition, the correlation between the surface morphology and adhesion is studied. To verify the importance of including the effect of the surface roughness in contact analysis and validate our hypothesis on the correlation between the surface morphology and adhesion, an extensive set of experiments was performed. In the experiments, a combination of the AFM peak-force mode (PFM) and the CP technique was employed to acquire a massive amount of information on cellulose-cellulose interactions by measuring the adhesion among six CSs of different sizes and a CM.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Research group: Micro and Nanosystems Research Group, BioMediTech, Harbin Institute of Technology, Tokyo University of Science

In this paper, we propose two novel methods for robot-world-hand-eye calibration and provide a comparative analysis against six state-of-the-art methods. We examine the calibration problem from two alternative geometrical interpretations, called 'hand-eye' and 'robot-world-hand-eye', respectively. The study analyses the effects of specifying the objective function as pose error or reprojection error minimization problem. We provide three real and three simulated datasets with rendered images as part of the study. In addition, we propose a robotic arm error modeling approach to be used along with the simulated datasets for generating a realistic response. The tests on simulated data are performed in both ideal cases and with pseudo-realistic robotic arm pose and visual noise. Our methods show significant improvement and robustness on many metrics in various scenarios compared to state-of-the-art methods.

Bioimpedance Sensor Array for Long-Term Monitoring of Wound Healing from Beneath the Primary Dressings and Controlled Formation of H2O2 Using Low-Intensity Direct Current

Chronic wounds impose a significant financial burden for the healthcare system. Currently, assessment and monitoring of hard-to-heal wounds are often based on visual means and measuring the size of the wound. The primary wound dressings must be removed before assessment can be done. We have developed a quasi-monopolar bioimpedance-measurement-based method and a measurement system to determine the status of wound healing. The objective of this study was to demonstrate that with an appropriate setup, long-term monitoring of wound healing from beneath the primary dressings is feasible. The developed multielectrode sensor array was applied on the wound area and left under the primary dressings for 142 h. The impedance of the wounds and the surrounding intact skin area was measured regularly during the study at 150 Hz, 300 Hz, 1 kHz, and 5 kHz frequencies. At the end of the follow-up period, the wound impedance had reached the impedance of the intact skin at the higher frequencies and increased significantly at the lowest frequencies. The measurement frequency affected the measurement sensitivity in wound monitoring. The skin impedance remained stable over the measurement period. The sensor array also enabled the administration of periodical low-intensity direct current (LIDC) stimulation in order to create an antimicrobial environment across the wound area via the controlled formation of hydrogen peroxide (H2O2).

Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts

Peroxy (RO
2
) and alkoxy (RO) radicals are prototypical intermediates in any hydrocarbon oxidation. In this work, we use computational methods to (1) study the mechanism and kinetics of the RO
2
+ OH reaction for previously unexplored "R" structures (R = CH(O)CH
2
and R = CH
3
C(O)) and (2) investigate a hitherto unaccounted channel of molecular growth, R′O
2
+ RO. On the singlet surface, these reactions rapidly form ROOOH and R′OOOR adducts, respectively. The former decomposes to RO + HO
2
and R(O)OH + O
2
products, while the main decomposition channel for the latter is back to the reactant radicals. Decomposition rates of R′OOOR adducts varied between 103 and 0.015 s
-1
at 298 K and 1 atm. The most long-lived R′OOOR adducts likely account for some fraction of the elemental compositions detected in the atmosphere that are commonly assigned to stable covalently bound dimers.

Energy-dependent diffusion in a soft periodic Lorentz gas

The periodic Lorentz gas is a paradigmatic model to examine how macroscopic transport emerges from microscopic chaos. It consists of a triangular lattice of circular hard scatterers with a moving point particle. Recently this system became relevant as a model for electronic transport in low-dimensional nanosystems such as molecular graphene. However, to more realistically mimic such dynamics, the hard Lorentz gas scatterers should be replaced by soft potentials. Here we study diffusion in a soft Lorentz gas with Fermi potentials under variation of the total energy of the moving particle. Our goal is to understand the diffusion coefficient as a function of the energy. In our numerical simulations we identify three different dynamical regimes: (i) the onset of diffusion at small energies; (ii) a transition where for the first time a particle reaches the top of the potential, characterized by the diffusion coefficient abruptly dropping to zero; and (iii) diffusion at high energies, where the diffusion coefficient increases according to a power law in the energy. All these different regimes are understood analytically in terms of simple random walk approximations.

Heterostructures of graphite/MoS2 display a wide range of lattice registry due to rotational alignment and/or lattice mismatch. Using high resolution scanning tunneling microscopy and spectroscopy (STM/STS) we investigated electronic properties of these heterostructures and observed changes in the bandgap as a function of the twist angle between the layers. Green's function based electronic structure calculations were carried out in order to shed light on the mechanism underlying the observed bandgap changes. Indirect coupling between the pz orbitals of the substrate Carbon atoms and the dz2 orbitals of the MoS2 layers (mediated by the pz orbitals of the bottom S layers) is found to be responsible for changes in the valence-band edge. Simple stacking of van der Waals materials with diverse properties have the potential to enable the fabrication of novel materials and device structures with tailored electronic properties.

Spin filtering in silicene by edges and chemically or electrically induced interfaces

Silicene is a graphene-like material with relatively strong spin-orbit coupling exhibiting gapless topologically protected edge states. In addition, it has a buckled structure, and hence, it stands as a feasible candidate for spintronic applications, where spin-polarized channels could be controlled with external electric fields realized with voltage gates attached to a Silicene sheet. Breaking the periodicity in 2D-materials with spin-orbit coupling produces one-dimensional edge and interface nanostructures that may give rise to an intrinsic locking of spin-polarization to electron momentum. We consider field induced and chemical ways to create interfaces to give way to spin polarized states for both zigzag and armchair alignments. While the spin polarization of a field induced interface channel can be feasibly tuned, a chemical interface is less flexibly tunable. However, controlling Fermi-level, e.g. with a gate voltage, might serve as a spin valve along the interface.

Mass balance control of crushing circuits

This paper describes a novel circuit-wide control scheme that addresses the challenging problem of mass balance control of crushing circuits. The control objective is to ensure 100% utilization at the circuit bottleneck and hence push the realized performance towards the theoretical maximum. The present control problem is challenging due to long transport delays, complex circuit layout, under-actuated process, several uncontrolled disturbance flows, varying number of active equipment, varying downstream demand, and changing bottleneck location. The proposed mass balance control scheme involves feeding the circuit according to actual demand and realized circuit throughput, whilst maintaining the amount of material accumulated into the circuit and ensuring the physical integrity of the circuit. Therefore, the circuit feeding is based on the realized processing capacity, rather than an individual bin level or an operator decision. To ensure the efficient use of available surge capacity, a limiting control structure is proposed to simultaneously realize the in-circuit multi-objective limit violation control and loose bin level control strategy. The proposed scheme offers a simple solution for the otherwise complex control problem, which can be easily and efficiently implemented using classic control methods. The paper details an entire design procedure, from the fundamental theory, through dynamic modeling and controller tuning, to the complete circuit control system design and implementation. The proposed scheme is evaluated under extensive full-scale and simulated experiments at various production scenarios and equipment combinations. The rigorous control experiments revealed that the proposed scheme delivered the desired behavior in every possible scenario. This enables the circuit to reach its true potential.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Automation Technology and Mechanical Engineering, Research group: Automation and Systems Theory, Chalmers University of Technology, University of Queensland

Analysis of GaAsBi growth regimes in high resolution with respect to As/Ga ratio using stationary MBE growth

The control of Bi incorporation and material properties in III-V-Bi alloys has proved challenging due to their high sensitivity to the epitaxial growth parameters. Here, we present a methodology for determining the variation in the Ga, As, and Bi fluxes and the temperature across a stationary substrate in molecular beam epitaxy. By correlating the flux distributions with material properties, we identify distinct regimes for epitaxy of GaAsBi. In particular, we devise a detailed image of the interplay between Bi incorporation and structural properties of a bulk GaAs
0.96
Bi
0.04
layer grown on GaAs(1 0 0) with respect to the As/Ga ratio. The influence of As/Ga is analyzed with high resolution over the important stoichiometric range (i.e. As/Ga = 0.6–1.6). Growth outside the near-stoichiometric As/Ga regime leads to decreased Bi incorporation, decreased structural quality and the formation of Ga, Ga/Bi or Bi droplets. On the other hand, growth at As/Ga = 1.00–1.17 leads to maximized material quality. For this regime, the surface roughness is further optimized by fine-tuning the As/Ga ratio to suppress surface mounding to a value of 0.5 nm. The results reveal the extreme sensitivity of GaAsBi growth to small variations in the As/Ga ratio, and demonstrate the applicability of stationary growth in studying these effects.

Hydrolysis and drug release from poly(ethylene glycol)-modified lactone polymers with open porosity

The ability to release active agents from a porous scaffold structure in situ enables the simultaneous structural support for the cells proliferating and differentiating towards tissue as well as the stimulation of tissue regeneration. Due to the great potentiality of such approach, drug-releasing scaffolds were fabricated from hydrolytically degradable polymers. Three copolymers of poly(ethylene glycol), ɛ-caprolactone, L- and D,L-lactide were synthesized and blended with bone-growth inducing active agents, dexamethasone (DM) and 2-phospho-L-ascorbic acid trisodium salt (AS). Porous scaffolds were prepared by means of super-critical carbon dioxide foaming. In the final scaffold structures, the particle size, location and the water solubility of the drug affected the release kinetics. As the large and water soluble AS particles were more exposed to the buffer solution compared to small DM particles, the AS release was burst-like whereas DM showed a long-term release. The material structure had a significant effect on the release kinetics as the porous scaffolds released active agents faster compared to the solid cylinders. Furthermore, this study showed the strong effect of polymer degradation and wettability on the release, which were more determinative than the pore architecture.

Today, the Intelligent Transportation Systems (ITS) are already in deep integration phase all over the world. One of the most significant enablers for ITS are vehicle positioning and tracking techniques. Worldwide integration of ITS employing Dedicated Short Range Communications (DSRC) and European standard for vehicular communication, known as ETSI ITS-G5, brings a variety of options to improve the positioning in areas where GPS connectivity is lacking precision. Utilization of the ready infrastructure, next-generation cellular 5G networks, and surrounding electronic devices together with conventional positioning techniques could become the solution to improve the overall ITS operation in vehicle-to-everything (V2X) communication scenario. Nonetheless, effective and secure communication protocols between the vehicle and roadside units should be both analyzed and improved in terms of potential attacks on the transmitted positioning-related data. In particular, said information might be misused or stolen at the infrastructure side conventionally assumed to be trusted. In this paper, we first survey different methods of vehicle positioning, which is followed by an overview of potential attacks on ITS systems. Next, we propose potential improvements allowing mutual authentication between the vehicle and infrastructure aiming at improving positioning data privacy. Finally, we propose a vision on the development and standardization aspects of such systems.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Electrical Engineering, St. Petersburg State University of Aerospace Instrumentation, ITMO University, Brno University of Technology

When exposed to air, alpha particles cause the production of light by exciting the molecules surrounding them. This light, the radioluminescence, is indicative of the presence of alpha radiation, thus allowing for the optical sensing of alpha radiation from distances larger than the few centimeters an alpha particle can travel in air. While the mechanics of radioluminescence in air and other gas compositions is relatively well understood, the same cannot be said about the radioluminescence properties of liquids. Better understanding of the radioluminescence properties of liquids is essential to design methods for the detection of radioactively contaminated liquids by optical means. In this article, we provide radioluminescence images of Am-241 dissolved in aqueous nitric acid (HNO
3
) solution and present the recorded radioluminescence spectrum with a maximum between and, and a steep decrease at the short wavelength side of the maximum. The shape of the spectrum resembles a luminescence process rather than Cerenkov light, bremsstrahlung, or other mechanisms with broadband emission. We show that the amount of light produced is about 150 times smaller compared to that of the same amount of Am-241 in air. The light production in the liquid is evenly distributed throughout the sample volume with a slight increase on the surface of the liquid. The radioluminescence intensity is shown to scale linearly with the Am-241 concentration and not be affected by the HNO
3
concentration.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, University of Helsinki, European Commission Joint Research Centre

The Devil Is in the Details: What Do We Really Track in Single-Particle Tracking Experiments of Diffusion in Biological Membranes?

Single-particle tracking (SPT) is an experimental technique that allows one to follow the dynamics of individual molecules in biological membranes with unprecedented precision. Given the importance of lipid and membrane protein diffusion in the formation of nanoscale functional complexes, it is critical to understand what exactly is measured in SPT experiments. To clarify this issue, we employed nanoscale computer simulations designed to match SPT experiments that exploit streptavidin-functionalized Au nanoparticles (AuNPs). The results show that lipid labeling interferes critically with the diffusion process; thus, the diffusion measured in SPT is a far more complex process than what has been assumed. It turns out that the influence of AuNP-based labels on the dynamics of probe lipids includes not only the AuNP-induced viscous drag that is the more significant the larger the NP but, more importantly, also the effects related to the interactions of the streptavidin linker with membrane lipids. Due to these effects, the probe lipid moves in a concerted manner as a complex with the linker protein and numerous unlabeled lipids, which can slow down the motion of the probe by almost an order of magnitude. Furthermore, our simulations show that nonlinker streptavidin tetramers on the AuNP surface are able to interact with the membrane lipids, which could potentially lead to multivalent labeling of the NPs by the probe lipids. Our results further demonstrate that in the submicrosecond time domain the motion of the probe lipid is uncorrelated with the motion of the AuNP, showing that there is a 1 μs limit for the temporal resolution of the SPT technique. However, this limit for the temporal resolution depends on the nanoparticle size and increases rapidly with growing AuNPs. Overall, the results provide a molecular-scale framework to accurately interpret SPT data and to design protocols that minimize label-induced artifacts.

Kinetics and thermochemistry of the reaction of 3-methylpropargyl radical with molecular oxygen

We have measured the kinetics and thermochemistry of the reaction of 3-methylpropargyl radical (but-2-yn-1-yl) with molecular oxygen over temperature (223-681 K) and bath gas density (1.2-15.0×1016cm-3) ranges employing photoionization mass-spectrometry. At low temperatures (223-304 K), the reaction proceeds overwhelmingly by a simple addition reaction to the -CH2 end of the radical, and the measured CH3CCCH2•+O2 reaction rate coefficient shows negative temperature dependence and depends on bath gas density. At intermediate temperatures (340-395 K), the addition reaction equilibrates and the equilibrium constant was determined at different temperatures. At high temperatures (465-681 K), the kinetics is governed by O2 addition to the third carbon atom of the radical, and rate coefficient measurements were again possible. The high temperature CH3CCCH2•+O2 rate coefficient is much smaller than at low T, shows positive temperature dependence, and is independent of bath gas density. In the intermediate and high temperature ranges, we observe a formation signal for ketene (ethenone). The reaction was further investigated by combining the experimental results with quantum chemical calculations and master equation modeling. By making small adjustments (2-3kJmol-1) to the energies of two key transition states, the model reproduces the experimental results within uncertainties. The experimentally constrained master equation model was used to simulate the CH3CCCH2•+O2 reaction system at temperatures and pressures relevant to combustion.

Unlike previously well-studied, acyclic pentacene oligomers, the first synthesis of a cyclic pentacene trimer with a fixed tubular conformation is reported. A short-step synthesis starting from common pentacenequinone yielded the target molecule with a 1.5 nanometer length and a subnanometer pore. Steady-state spectroscopic analyses revealed that the close proximity of the non-conjugated, three pentacene chromophores allows the nanotube to display stepwise electrochemical/chemical oxidation characteristics. Furthermore, time-resolved transient absorption measurements elucidated the generation of an excited triplet state of the nanotube, with high quantum yield reaching about 180 % through intramolecular singlet fission and a very long triplet lifetime.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Tokyo Institute of Technology, University of Yamanashi, Keio University

We employ atomic layer deposition to prepare 50 nm thick hematite photoanodes followed by passivating them with a 0.5 nm thick Ta
2
O
5
-overlayer and compare them with samples uniformly doped with the same amount of tantalum. We observe a three-fold improvement in photocurrent with the same onset voltage using Ta-overlayer hematite photoanodes, while electrochemical impedance spectroscopy under visible light irradiation shows a decreased amount of surface states under water splitting conditions. The Ta-doped samples have an even higher increase in photocurrent along with a 0.15 V cathodic shift in the onset voltage and decreased resistivity. However, the surface state capacitance for the Ta-doped sample is twice that of the reference photoanode, which implies a larger amount of surface hole accumulation. We further utilize transient absorption spectroscopy in the sub-millisecond to second timescale under operating conditions to show that electron trapping in both Ta
2
O
5
-passivated and Ta-doped samples is markedly reduced. Ultrafast transient absorption spectroscopy in the sub-picosecond to nanosecond timescale shows faster charge carrier dynamics and reduced recombination in the Ta-doped hematite photoanode resulting in the increased photoelectrochemical performance when compared with the Ta
2
O
5
-overlayer sample. Our results show that passivation does not affect the poor charge carrier dynamics intrinsic to hematite based photoanodes. The Ta-doping strategy results in more efficient electron extraction, solving the electron trapping issue and leading to increased performance over the surface passivation strategy.

Many genetic reporter systems require molecular oxygen; therefore, the use of reporter genes to study molecular mechanisms in anaerobic microorganisms has been hampered by the lack of convenient reporting systems. We describe reporter gene whole cell-based biosensor systems based on luciferase genes and the associated oxygen-requiring enzymes. By using two different oxygen-dependent reporters, insect and bacterial luciferases, and two bacterial hosts, Gram (+) Bifidobacterium longum and Gram (-) Escherichia coli, we show that the enzymes can be used in gene expression studies of anaerobic bacteria. E. coli, a facultative anaerobe, was grown both in aerobic and anaerobic conditions with an arabinose-inducible expression system. We show that a short treatment time of few minutes in ambient atmosphere is sufficient to detect light emission from living cells that is directly proportional to the number of cells and to the inducer concentration. The induction levels were the same in both the aerobically and anaerobically cultured cells. Similar results were obtained in the case of B. longum cultured in anaerobic conditions.

An automated algorithm for reliable equation of state fitting of magnetic systems

In computational physics and materials science ground-state properties are often extracted from an equation of state fit to energy-volume data. Magnetic systems often have multiple magnetic phases present in the energy-volume data, which poses a challenge for the fitting approach because the results are sensitive to the selection of included fitting points. This is because practically all popular equation of state fitting functions, such as Murnaghan and Birch-Murnaghan, assume just one phase and therefore cannot correctly fit magnetic energy-volume data that contains multiple phases. When fitting magnetic energy-volume data it is therefore important to select the range of fitting points in such a way that only points from the one relevant phase are included. We present a simple algorithm that makes the point selection automatically. Selecting fitting points automatically removes human bias and should also be useful for large-scale projects where selecting all fitting points by hand is not feasible.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, Research area: Computational Physics, Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, Hungarian Academy of Sciences, Uppsala University, Department of Physics and Astronomy, University of Turku, Royal Institute of Technology

We report the formation of a new class of solvent-intercalated two-dimensional (SI-2D) formamidinium lead halide perovskites. They can be mixed with three-dimensional (3D) stoichiometric perovskites by controlling the ratio of the precursor solutions. The composite leads to greatly improved photoluminescence quantum yield (PLQY) over the 3D compound. The enhanced PLQY is attributed to a type-I band alignment between the 3D and SI-2D, as revealed by first-principles calculations, which results in confined excitons with enhanced radiative recombination. The films exhibited excellent thermal and air stability retaining PLQY > 20% over 2 months in ambient conditions. Assemblies of halide perovskites with mixed dimensionality offer a pathway to enhance optoelectronic performance and device lifetimes.

Tuning of nonlinear absorption in highly luminescent CdSe based quantum dots with core-shell and core/multi-shell architectures

We present our effort on an efficient way of tuning the nonlinear absorption mechanisms in ultra-small CdSe based quantum dots by implementing core-shell and core/multi-shell architectures. Depending on the size, architecture and composition of the QDs, these materials exhibited resonant and near-resonant nonlinear optical absorption properties such as saturable (SA) and reverse saturable (RSA) absorption for 5 ns pulses of 532 nm. These QDs exhibited a non-monotonic dependence of the effective two-photon absorption coefficient (β) under nanosecond excitation with a maximum value for a thinner shell. We obtained a nonlinear absorption enhancement of an order of magnitude by adopting the core-shell architecture compared to their individual counterparts. Interestingly, CdSe QDs exhibit SA and/or RSA depending on their size and show a switching over from SA to RSA as the input intensity increases. We explained the enhanced nonlinear absorption in core-shell QDs compared to their individual counterparts in view of enhanced local fields associated with the core-shell structure. Thus, the present nanostructured materials are excellent candidates as saturable absorbers and optical limiters.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, University of Johannesburg, Mahatma Gandhi University, Qatar University, Laboratory of Photonics, University of Concepcion

Multiphoton Excitation of CsPbBr3 Perovskite Quantum Dots (PQDs): How Many Electrons Can One PQD Donate to Multiple Molecular Acceptors?

Metastable multiexcitonic states (MESs) of semiconductor quantum dots can be involved in multielectron transfer reactions, which opens new perspectives in nanomaterials-based optoelectronic applications. Herein, we demonstrate the generation of a MES in CsPbBr3 perovskite quantum dots (PQDs) and its dissociation dynamics through multiple electron transfers to molecular electron acceptors, anthraquinones (AQs), bound to the PQD surface by a carboxylic anchor. As many as 14 excitons are produced at an excitation density of roughly 220 μJ cm-2 without detectable PQD degradation. Addition of AQ results in the formation of PQD-AQ hybrids with excess of AQs (PQD:AQ ≈ 1:20), which opens the possibility of multielectron transfer acts from MES to AQs. We found that the electron transfer saturates after roughly five transfer acts and that the first electron transfer (ET) time constant is as short as 1 ps. However, each ET increases the Coulomb potential barrier for the next ET, which decreases the rate of ET, resulting in a saturation after five ETs.

Spodumene tailings for porcelain and structural materials: Effect of temperature (1050–1200 °C) on the sintering and properties

The use of industrial by-products as substitute to conventional natural resources in ceramic production is of interest from an environment preservation and solid wastes management. This paper deals with the recycling of tailings from spodumene concentration during lithium production (Quartz Feldspar Sand; QFS), for the production of porcelain and structural materials. The QFS obtained from spodumene processing consisted mainly of quartz, albite, microcline with traces of muscovite. Mixtures of QFS and standard porcelain ingredients were sintered at 1050–1200 °C at 50 °C intervals and their properties were compared with a conventional porcelain composition prepared under the same conditions. Phase composition was assessed by XRD analysis using Rietveld refinement. Tests such as water absorption, apparent density, sintering shrinkage, compressive and flexural strength were used for physical comparison. The results showed that higher densification was achieved at 1200 °C, with a drastic reduction of water absorption below 1%. A compressive strength of 40 MPa was obtained at 1050 °C in the composition made of 50 wt% QFS and 50 wt% kaolin, increasing to 85 MPa at 1100 °C. The strength increase was attributed to better glassy phase formation and mullite growth. The QFS was found to contain no hazardous elements and showed promising sintering results, indicating its high suitability to substitute conventional resources in the production of ceramic materials.

The removal of volatile fatty acids was examined through adsorption on anion exchange resins in batch systems. During the initial screening step, granular activated carbon and 11 anion exchange resins were tested and the resins Amberlite IRA-67 and Dowex optipore L-493 were chosen for further investigation. The adsorption kinetics and diffusion mechanism and adsorption isotherms of the two resins for VFA were evaluated. Based on the selective adsorption capacity of the resins, a sequential batch process was tested to achieve separation of acetic acid from the VFA mixture and selective recoveries > 85% acetic acid and ~ 75% propionic acid was achieved.

General information

Publication status: E-pub ahead of print

MoE publication type: A1 Journal article-refereed

Organisations: Materials Science and Environmental Engineering, Hydraulic and Environmental Engineering (IHE) Inst. for Water Education, Institute for Water Education

Possible strategy to use differential mobility spectrometry in real time applications

Differential Mobility Spectrometry (DMS), also called as FAIMS is a variation of atmospheric pressure ion mobility measurement techniques and is capable of providing information about the electric field - mobility dependence of ions. In this method, a combined electric field is used. This field consists of asymmetric oscillating electric field of high intensity and low static field component. Analytical information in DMS is 2-dimensional dependence of ionic current on oscillating field amplitude and the value of static field intensity. The measurement of DMS signal for whole ranges of both variables is time consuming and also generates lot of data. It is a disadvantage of DMS method, which limits the use of this otherwise powerful technology in real time applications that require a response time of few seconds. This paper presents a way to limit measurement time by heuristic knowledge of the properties of the data space and another method based on the concept of Shannon Entropy to find operating parameters satisfying both separation and signal to noise ratio requirements.

General information

Publication status: E-pub ahead of print

MoE publication type: A1 Journal article-refereed

Organisations: BioMediTech, Tampere University Hospital, Military University of Technology, Department of Surgery, Tampere University of Applied Sciences, LappeenrantaLahti University of Technology LUT

The preparation of unprecedented 6,12-disubstituted methanodibenzo[b,f ][1,5]dioxocins from pyrrolidine catalyzed self-condensation of 2′-hydroxyacetophenones is herein described. This method provides easy access to this highly bridged complex core, resulting in construction of two C-O and two C-C bonds, a methylene bridge and two quaternary centers in a single step. The intricate methanodibenzo[b,f ][1,5]dioxocin compounds were obtained in up to moderate yields after optimization of the reaction conditions concerning solvent, reaction times and the use of additives. Several halide substituted methanodibenzo[b,f ][1,5]dioxocins could be prepared from correspondent 2′-hydroxyacetophenones.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Materials Science and Environmental Engineering, Faculdade de Farmacia da Universidade de Lisboa, University of Jyvaskyla

Endophytes are microorganisms living inside plant hosts and are known to be beneficial for the host plant vitality. In this study, we isolated three endophytic fungus species from the roots of Scots pine seedlings growing on Finnish drained peatland setting. The isolated fungi belonged to dark septate endophytes (DSE). The metabolic profiles of the hot water extracts of the fungi were investigated using Ultrahigh Performance Liquid Chromatography with Diode Array Detection and Electron Spray Ionization source Mass Spectrometry with Orbitrap analyzer (UPLC–DAD–ESI–MS–Orbitrap). Out of 318 metabolites, we were able to identify 220, of which a majority was amino acids and peptides. Additionally, opine amino acids, amino acid quinones, Amadori compounds, cholines, nucleobases, nucleosides, nucleotides, siderophores, sugars, sugar alcohols and disaccharides were found, as well as other previously reported metabolites from plants or endophytes. Some differences of the metabolic profiles, regarding the amount and identity of the found metabolites, were observed even though the fungi were isolated from the same host. Many of the discovered metabolites have been described possessing biological activities and properties, which may make a favorable contribution to the host plant nutrient availability or abiotic and biotic stress tolerance.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Materials Science and Environmental Engineering, Research group: Bio- and Circular Economy, Natural Resources Institute Finland (Luke), Turku University of Applied Science, University of Helsinki, School of Chemical Engineering, Aalto University

Bibliographical note

Exclusive occurrence of photoinduced energy transfer and switching of its direction by rectangular π-extension of nanographenes

As structure defined cutouts of the graphene lattice, nanographene molecules have gained plenty of attention because of their high potential for versatile applications in organic electronics and energy conversion devices and as ideal model systems for the better understanding of intrinsic structure-property correlations of graphenes. In this study, well-defined nanographenes with sp2 carbon networks of different sizes, hexa-peri-hexabenzocoronene (HBC) and its rectangularly π-extended version, a short graphene nanoribbon (GNR), have been covalently functionalized with photoactive porphyrin molecules. On the basis of their spectroscopic studies, the photodynamics of the porphyrin-linked nanographenes was found to be influenced substantially by the size of the nanographenes. Photoexcitation of the porphyrin-HBC linked system led to exclusive energy transfer (EnT) from the first singlet excited state (S1) of the nanographene to the porphyrin, whereas opposite selective EnT occurred from the first and second singlet excited states (S1 and S2) of the porphyrin to the nanographene in the porphyrin-GNR linked system. In particular, ultrafast efficient EnTs from both the S2 and S1 states of the porphyrin to GNR mimic the corresponding ultrafast EnTs from the S2 and S1 states of carotenoids to chlorophylls in light-harvesting systems of natural photosynthesis. Such unique photophysical properties will be useful for the rational design of carbon-based photofunctional nanomaterials for optoelectronics and solar energy conversion devices.

The maximum Hosoya index of unicyclic graphs with diameter at most four

The Hosoya index of a graph is defined by the total number of the matchings of the graph. In this paper, we determine the maximum Hosoya index of unicyclic graphs with n vertices and diameter 3 or 4. Our results somewhat answer a question proposed by Wagner and Gutman in 2010 for unicyclic graphs with small diameter.

The Hosoya entropy of graphs revisited

In this paper we extend earlier results on Hosoya entropy (H-entropy) of graphs, and establish connections between H-entropy and automorphisms of graphs. In particular, we determine the H-entropy of graphs whose automorphism group has exactly two orbits, and characterize some classes of graphs with zero H-entropy.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Research group: Computational Medicine and Statistical Learning Laboratory (CMSL), Computing Sciences, Research group: Predictive Society and Data Analytics (PSDA), Shahid Rajaee Teacher Training University, University of Applied Sciences Upper Austria, School of Management, Hall in Tyrol, Nankai University, The City College of New York (CUNY), Aalto University, Peking University

The decrease of stress at constant strain, that is, the stress relaxation process as a function of temperature, is a central mechanical characteristics of elastomer nanocomposites for their potential applications. However, in the conventional stress relaxation test, the relaxation behavior is usually determined as a function of time at constant temperature. The present work reports the temperature scanning stress relaxation (TSSR) characteristics of a new kind of mechanically adaptive elastomer nanocomposite by monitoring the nonisothermal relaxation behavior as a function of temperature. This kind of adaptive elastomer nanocomposite was prepared by introducing calcium sulfate (CaSO4), as the water-responsive phase into the hydrophilic elastomer matrix. The influence of water-induced structural changes on TSSR behavior was investigated. Water treatment had a strong effect on the shape of the relaxation spectrum of the nanocomposite. It was revealed that the in situ development of hydrated nano-rod crystal structures of CaSO4 in the elastomer matrix was responsible for the changes in the mechanical relaxation behavior of the composites. Atomic force microscopy was used to verify this nano-rod crystal morphology in the elastomer matrix. The mechanism of water-induced mechanical reinforcement of the composite was explored from dynamic mechanical analysis of the material and correlated with its stress relaxation behavior.

As the Earth's atmosphere contains an abundant amount of water as vapors, a device which can capture a fraction of this water could be a cost-effective and practical way of solving the water crisis. There are many biological surfaces found in nature which display unique wettability due to the presence of hierarchical micro-nanostructures and play a major role in water deposition. Inspired by these biological microstructures, we present a large scale, facile and cost-effective method to fabricate water-harvesting functional surfaces consisting of high-density copper oxide nanoneedles. A controlled chemical oxidation approach on copper surfaces was employed to fabricate nanoneedles with controlled morphology, assisted by bisulfate ion adsorption on the surface. The fabricated surfaces with nanoneedles displayed high wettability and excellent fog harvesting capability. Furthermore, when the fabricated nanoneedles were subjected to hydrophobic coating, these were able to rapidly generate and shed coalesced droplets leading to further increase in fog harvesting efficiency. Overall, ∼99% and ∼150% increase in fog harvesting efficiency was achieved with non-coated and hydrophobic layer coated copper oxide nanoneedle surfaces respectively when compared to the control surfaces. As the transport of the harvested water is very important in any fog collection system, hydrophilic channels inspired by leaf veins were made on the surfaces via a milling technique which allowed an effective and sustainable way to transport the captured water and further enhanced the water collection efficiency by ∼9%. The system presented in this study can provide valuable insights towards the design and fabrication of fog harvesting systems, adaptable to arid or semi-arid environmental conditions.

Semihydrogenation of acetylene (SHA) in an ethylene-rich stream is an important process for polymer industries. Presently, Pd-based catalysts have demonstrated good acetylene conversion (XC2H2), however, at the expense of ethylene selectivity (SC2H4). In this study, we have employed a systematic approach using density functional theory (DFT) to identify the best catalyst in a Cu-Pt system. The DFT results showed that with a 55 atom system at ∼1.1 Pt/Cu ratio for Pt28Cu27/Al2O3, the d-band center shifted -2.2 eV relative to the Fermi level leading to electron-saturated Pt, which allows only adsorption of ethylene via a π-bond, resulting in theoretical 99.7% SC2H4 at nearly complete XC2H2. Based on the DFT results, Pt-Cu/Al2O3 (PtCu) and Pt/Al2O3 (Pt) nanocatalysts were synthesized via cluster beam deposition (CBD), and their properties and activities were correlated with the computational predictions. For bimetallic PtCu, the electron microscopy results show the formation of alloys. The bimetallic PtCu catalyst closely mimics the DFT predictions in terms of both electronic structure, as confirmed by X-ray photoelectron spectroscopy, and catalytic activity. The alloying of Pt with Cu was responsible for the high C2H4 specific yield resulting from electron transfer between Cu and Pt, thus making PtCu a promising catalyst for SHA.

General information

Publication status: E-pub ahead of print

MoE publication type: A1 Journal article-refereed

Organisations: Physics, Research group: Materials and Molecular Modeling, INL - International Iberian Nanotechnology, University of Swansea, Edifici CM3, Iowa State University, U.S. Department of Energy, Catalan Institute for Research and Advanced Studies (ICREA)

How well can we predict cluster fragmentation inside a mass spectrometer?

Fragmentation of molecular clusters inside mass spectrometers is a significant source of uncertainty in a wide range of chemical applications. We have measured the fragmentation of sulfuric acid clusters driving atmospheric new-particle formation, and developed a novel model, based on first principles calculations, capable of quantitatively predicting the extent of fragmentation.

Reversible photodoping of TiO2 nanoparticles

Observations on strong photochromic effect of crystalline TiO2 quantum dots (mean size ≈ 4 nm) are presented. The synthesized quantum dots consist of irregularly shaped anatase TiO2 nanoparticles (NPs) and are dispersed in butanol (8 % by mass). Obtained NPs exhibit a dramatic photo-response to UV light, enabling effective transmittance modula-tion of in a broad wavelength range extending from visible to near-infrared region, and even the thermal black body radiation regime beyond 10 μm. The exceptional photo-response is attributed to hole-scavenging by butanol, TiO2 self-reduction, injection of electrons to the conduction band, and consequent localized surface plasmon resonances in NPs. Observed optical effect is reversible and the initial high transmittance state can be restored simply by exposing the NPs to air. Applied NP synthesis route is economic and can be easily scaled for applications such as smart window technol-ogies.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Photonics, Research group: Surface Science, Univ Tartu, University of Tartu, University of Tartu Institute of Physics, Inst Phys, University of Tartu

Bibliographical note

Less Is More: Enhancement of Second-Harmonic Generation from Metasurfaces by Reduced Nanoparticle Density

We investigate optical second-harmonic generation (SHG) from metasurfaces where noncentrosymmetric V-shaped gold nanoparticles are ordered into regular array configurations. In contrast to expectations, a substantial enhancement of the SHG signal is observed when the number density of the particles in the array is reduced. More specifically, by halving the number density, we obtain over 5-fold enhancement in SHG intensity. This striking result is attributed to favorable interparticle interactions mediated by the lattice, where surface-lattice resonances lead to spectral narrowing of the plasmon resonances. Importantly, however, the results cannot be explained by the improved quality of the plasmon resonance alone. Instead, the lattice interactions also lead to further enhancement of the local fields at the particles. The experimental observations agree very well with results obtained from numerical simulations including lattice interactions.

Experimental moment resistance of rectangular hollow section T joints

Resistance is the main property of tubular joints. The determination of the joint resistance from the experimental load-deformation curve always represents a challenging task. Currently there are two main methods to find the experimental resistance, which are called plastic and ultimate resistance. However, there is no single opinion on which one should be commonly used. Based on the experimental results, this paper directly compares the two existed approaches. The study is restricted to welded square hollow section T joints under in-plane bending moment. The paper considers only the joints with β < 0.85, i.e. when the behaviour of the joint is governed by chord face failure. The results show that plastic resistance leads to more conservative results than ultimate resistance, providing thus safer results. However, attention should be also paid to the difference between the labour intensity of the presented methods.

Actin polymerization powers key cellular processes, including motility, morphogenesis, and endocytosis. The actin turnover cycle depends critically on "re-charging" of ADP-Actin monomers with ATP, but whether this reaction requires dedicated proteins in cells, and the underlying mechanism, have remained elusive. Here we report that nucleotide exchange catalyzed by the ubiquitous cytoskeletal regulator cyclase-Associated protein (CAP) is critical for actin-based processes in vivo. We determine the structure of the CAP-Actin complex, which reveals that nucleotide exchange occurs in a compact, sandwich-like complex formed between the dimeric actin-binding domain of CAP and two ADP-Actin monomers. In the crystal structure, the C-Terminal tail of CAP associates with the nucleotide-sensing region of actin, and this interaction is required for rapid re-charging of actin by both yeast and mammalian CAPs. These data uncover the conserved structural basis and biological role of protein-catalyzed re-charging of actin monomers.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, University of Helsinki Institute of Biotechnology, Brandeis University

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Photonics, Research group: Nonlinear Optics, University “Roma Tre”, University of Southampton, Case Western Reserve University, CNR-NANOTEC & University of Calabria, Institute for Complex Systems

Machine learning plastic deformation of crystals

Plastic deformation of micron-scale crystalline solids exhibits stress-strain curves with significant sample-to-sample variations. It is a pertinent question if this variability is purely random or to some extent predictable. Here we show, by employing machine learning techniques such as regression neural networks and support vector machines that deformation predictability evolves with strain and crystal size. Using data from discrete dislocations dynamics simulations, the machine learning models are trained to infer the mapping from features of the pre-existing dislocation configuration to the stress-strain curves. The predictability vs strain relation is non-monotonic and exhibits a system size effect: larger systems are more predictable. Stochastic deformation avalanches give rise to fundamental limits of deformation predictability for intermediate strains. However, the large-strain deformation dynamics of the samples can be predicted surprisingly well.

Modifiable hydrogels have revealed tremendous insight into how physical characteristics of cells’ 3D environment drive stem cell lineage specification. However, in native tissues, cells do not passively receive signals from their niche. Instead they actively probe and modify their pericellular space to suit their needs, yet the dynamics of cells’ reciprocal interactions with their pericellular environment when encapsulated within hydrogels remains relatively unexplored. Here, we show that human bone marrow stromal cells (hMSC) encapsulated within hyaluronic acid-based hydrogels modify their surroundings by synthesizing, secreting and arranging proteins pericellularly or by degrading the hydrogel. hMSC’s interactions with this local environment have a role in regulating hMSC fate, with a secreted proteinaceous pericellular matrix associated with adipogenesis, and degradation with osteogenesis. Our observations suggest that hMSC participate in a bi-directional interplay between the properties of their 3D milieu and their own secreted pericellular matrix, and that this combination of interactions drives fate.

Aminobenzylated 4-Nitrophenols as Antibacterial Agents Obtained from 5-Nitrosalicylaldehyde through a Petasis Borono-Mannich Reaction

Multidrug-resistant bacteria are one of the current biggest threats to public health and are responsible for most nosocomial infections. Herein, we report the efficient and facile synthesis of antibacterial agents aminoalkylphenols, derived from 5-nitrosalicyladehyde and prepared through a Petasis borono-Mannich multicomponent reaction. Minimum inhibitory concentrations (MICs) as low as 1.23 μM for a chlorine derivative were determined for multidrug-resistant Gram-positive bacteria, namely, Staphylococcus aureus and Enterococcus faecalis, two of the main pathogens responsible for infections in a hospital environment. The most promising antibacterial agents were further tested against eight strains of four Gram-positive species in order to elucidate their antibacterial broadness. In vitro cytotoxicity assays of the most active aminoalkylphenol revealed considerably lower toxicity against mammalian cells, as concentrations one order of magnitude higher than the determined MICs were required to induce human keratinocyte cell death. The phenol moiety was verified to be important in deeming the antibacterial properties of the analyzed compounds, although no correlation between such properties and their antioxidant activity was observed. A density functional theory computational study substantiated the ability of aminoalkylphenols to serve as precursors of ortho-quinone methides.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Research group: Chemistry & Advanced Materials, CBIOS-Universidade Lusófona Research Center for Biosciences and Health Technologies, National Institute of Health, Faculdade de Farmacia da Universidade de Lisboa

A central research area in nonlinear science is the study of instabilities that drive extreme events. Unfortunately, techniques for measuring such phenomena often provide only partial characterisation. For example, real-time studies of instabilities in nonlinear optics frequently use only spectral data, limiting knowledge of associated temporal properties. Here, we show how machine learning can overcome this restriction to study time-domain properties of optical fibre modulation instability based only on spectral intensity measurements. Specifically, a supervised neural network is trained to correlate the spectral and temporal properties of modulation instability using simulations, and then applied to analyse high dynamic range experimental spectra to yield the probability distribution for the highest temporal peaks in the instability field. We also use unsupervised learning to classify noisy modulation instability spectra into subsets associated with distinct temporal dynamic structures. These results open novel perspectives in all systems exhibiting instability where direct time-domain observations are difficult.

High Nitrogen Removal in a Constructed Wetland Receiving Treated Wastewater in a Cold Climate

Constructed wetlands provide cost-efficient nutrient removal, with minimal input of human labor and energy, and their number is globally increasing. However, in northern latitudes, wetlands are rarely utilized, because their nutrient removal efficiency has been questioned due to the cold climate. Here, we studied nutrient retention and nitrogen removal in a boreal constructed wetland (4-ha) receiving treated nitrogen-rich wastewater. On a yearly basis, most of the inorganic nutrients were retained by the wetland. The highest retention efficiency was found during the ice-free period, being 79% for ammonium-nitrogen (NH4+-N), 71% for nitrate-nitrogen (NO3--N), and 88% for phosphate-phosphorus (PO43--P). Wetland also acted as a buffer zone during the disturbed nitrification process of the wastewater treatment plant. Denitrification varied between 106 and 252 mg N m-2 d-1 during the ice-free period. During the ice-cover period, total gaseous nitrogen removal was 147 mg N m-2 d-1, from which 66% was removed as N2, 28.5% as N2O through denitrification, and 5.5% as N2 through anammox. Nearly 2600 kg N y-1 was estimated to be removed through microbial gaseous N-production which equaled 72% of NO3--N and 60% of TN yearly retention in the wetland. The wetland retained nutrients even in winter, when good oxygen conditions prevailed under ice. The results suggest that constructed wetlands are an efficient option for wastewater nitrogen removal and nutrient retention also in cold climates.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Research group: Bio- and Circular Economy, University of Helsinki, Jyväskylän yliopisto, University of Eastern Finland

High-Yield Generation of Triplet Excited States by an Efficient Sequential Photoinduced Process from Energy Transfer to Singlet Fission in Pentacene-Modified CdSe/ZnS Quantum Dots

Singlet fission (SF) is expected to improve photoenergy conversion systems by generating two electrons from one photon. Pentacenes meet the energy-level matching condition between a singlet and two triplet states: [E(S1)≥2E(T1)]. However, the molar absorption coefficients of pentacenes in the approximately 400–500 nm region are limited, whereas quantum dots, such as CdSe/ZnS (QD), possess high fluorescence quantum yields and particle-size-dependent fluorescence wavelengths. Thus, a combination of QD (D) and pentacene (A) provides a system of both an enhanced light-harvesting efficiency throughout the solar spectrum and an efficient conversion of the harvested light into the triplet states by SF. Based on these points, m-phenylene-bridged triisopropylsilane (TIPS)-pentacene dimer-functionalized QD (denoted as m-(Pc)2-QD) was synthesized to examine the sequential photoinduced process from energy transfer to SF. In femtosecond transient absorption measurements, initial energy transfer from QD to pentacene (quantum yield: 87 %) and subsequent SF were efficiently observed. The quantum yield of triplet states of pentacene units (ΦΤ) based on the excitation of QD attained is 160±6.7 %.

M2M Communication Assessment in Energy-Harvesting and Wake-Up Radio Assisted Scenarios Using Practical Components

Techniques for wireless energy harvesting (WEH) are emerging as a fascinating set of solutions to extend the lifetime of energy-constrained wireless networks, and are commonly regarded as a key functional technique for almost perpetual communications. For example, with WEH technology, wireless devices are able to harvest energy from different light sources or Radio Frequency (RF) signals broadcast by ambient or dedicated wireless transmitters to support their operation and communications capabilities. WEH technology will have increasingly wider range of use in upcoming applications such as wireless sensor networks, Machine-to-Machine (M2M) communications, and the Internet of Things. In this paper, the usability and fundamental limits of joint RF and solar cell or photovoltaic harvesting based M2M communication systems are studied and presented. The derived theoretical bounds are in essence based on the Shannon capacity theorem, combined with selected propagation loss models, assumed additional link nonidealities, diversity processing, as well as the given energy harvesting and storage capabilities. Fundamental performance limits and available capacity of the communicating link are derived and analyzed, together with extensive numerical results evaluated in different practical scenarios, including realistic implementation losses and state-of-the-art printed supercapacitor performance figures with voltage doubler-based voltage regulator. In particular, low power sensor type communication applications using passive and semi-passive wake-up radio (WuR) are addressed in the study. The presented analysis principles and results establish clear feasibility regions and performance bounds for wireless energy harvesting based low rate M2M communications in the future IoT networks.

Molecular-Scale Ligand Effects in Small Gold-Thiolate Nanoclusters

Because of the small size and large surface area of thiolate-protected Au nanoclusters (NCs), the protecting ligands are expected to play a substantial role in modulating the structure and properties, particularly in the solution phase. However, little is known on how thiolate ligands explicitly modulate the structural properties of the NCs at atomic level, even though this information is critical for predicting the performance of Au NCs in application settings including as a catalyst interacting with small molecules and as a sensor interacting with biomolecular systems. Here, we report a combined experimental and theoretical study, using synchrotron X-ray spectroscopy and quantum mechanics/molecular mechanics simulations, that investigates how the protecting ligands impact the structure and properties of small Au18(SR)14 NCs. Two representative ligand types, smaller aliphatic cyclohexanethiolate and larger hydrophilic glutathione, are selected, and their structures are followed experimentally in both solid and solution phases. It was found that cyclohexanethiolate ligands are significantly perturbed by toluene solvent molecules, resulting in structural changes that cause disorder on the surface of Au18(SR)14 NCs. In particular, large surface cavities in the ligand shell are created by interactions between toluene and cyclohexanethiolate. The appearance of these small molecule-accessible sites on the NC surface demonstrates the ability of Au NCs to act as a catalyst for organic phase reactions. In contrast, glutathione ligands encapsulate the Au NC core via intermolecular interactions, minimizing structural changes caused by interactions with water molecules. The much better protection from glutathione ligands imparts a rigidified surface and ligand structure, making the NCs desirable for biomedical applications due to the high stability and also offering a structural-based explanation for the enhanced photoluminescence often reported for glutathione-protected Au NCs.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, Dalhousie University, Universitat Autonoma de Barcelona, Spain, Catalan Institute for Research and Advanced Studies (ICREA), Carnegie Mellon University, National University of Singapore, Norwegian Univ. of Sci. and Technol.

This study investigated the removal of selenate (SeO42−), sulfate (SO42−) and nitrate (NO3−) at different influent pH values ranging from 7.0 to 5.0 and 20 °C in an upflow anaerobic sludge blanket (UASB) reactor using lactate as an electron donor. At pH 5.0, the UASB reactor showed a 20–30% decrease in reactor performance compared to operation at pH 5.5 to 7.0, reaching removal efficiencies of 79%, 15%, 43% and 61% for NO3−, SO42−, Setotal and Sediss, respectively. However, the reactor stability was an issue upon lowering the pH to 5.0 and further experiments are recommended. The sludge formed during low pH operation had a fluffy, floc-like appearance with filamentous structure, possibly due to the low polysaccharide (PS) to protein (PN) ratio (0.01 PS/PN) in the soluble extracellular polymeric substances (EPS) matrix of the biomass. Scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDX) analysis of the sludge confirmed Se oxyanion reduction and deposition of Se0 particles inside the biomass. Microbial community analysis using Illumina MiSeq sequencing revealed that the families of Campylobacteraceae and Desulfomicrobiaceae were the dominant phylotypes throughout the reactor operation at approximately 23% and 10% relative abundance, respectively. Furthermore, approximately 10% relative abundance of both Geobacteraceae and Spirochaetaceae was observed in the granular sludge during the pH 5.0 operation. Overall, this study demonstrated the feasibility of UASB operation at pH values ranging from 7.0 to 5.0 for removing Se and other oxyanions from wastewaters.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Bhabha Atomic Research Centre, Montana State University (MSU), Hydraulic and Environmental Engineering (IHE) Inst. for Water Education

Tribocorrosion behaviour of aluminium bronze CuAl10Fe5Ni5 in 3.5 wt.% NaCl solution was investigated in a pin-on-disc facility containing an electrochemical cell. Oxidising capacity and contact pressure to alumina counterbody were varied. Pure corrosion occurred as selective dissolution of α phase included in the eutectoid structure. Contact to counterbody introduced plastic deformation, extrusion of the material and abrasive wear. Wear-corrosion interactions varied between the two contact pressures, with lower material losses appearing at the higher pressure. The significant acceleration of material degradation by the interactions was not clearly reflected to kinetics or thermodynamics of corrosion. These results are presented and discussed here.

We demonstrate computation of total dynamic multipole polarizabilities using path-integral Monte Carlo method (PIMC). The PIMC approach enables accurate thermal and nonadiabatic mixing of electronic, rotational, and vibrational degrees of freedom. Therefore, we can study the thermal effects, or lack thereof, in the full multipole spectra of the chosen one- and two-electron systems: H, Ps, He, Ps2, H2, and HD+. We first compute multipole-multipole correlation functions up to octupole order in imaginary time. The real-domain spectral function is then obtained by analytical continuation with the maximum entropy method. In general, sharpness of the active spectra is limited, but the obtained off-resonant polarizabilities are in good agreement with the existing literature. Several weak and strong thermal effects are observed. Furthermore, the polarizabilities of Ps2 and some higher multipole and higher frequency data have not been published before. In addition, we compute isotropic dispersion coefficients C6, C8, and C10 between pairs of species using the simplified Casimir-Polder formulas.

Understanding the electrochemical properties of bio-anodes is essential to improve performance of bioelectrochemical systems. Electrochemical Impedance Spectroscopy (EIS) is often used to study these properties in detail. Analysis of the EIS response, however, is challenging due to the interfering effect of the large capacitance of typically used graphite and carbon-based electrodes. In this study, we used flat electrodes made of conductive Fluorine-doped Tin Oxide (FTO) as anode, and monitored bio-anode performance. We show that with this configuration, it is possible to accurately separate the distinct contributions to the electrical response of the bio-anodes: charge transfer, biofilm and diffusion resistances, and biofilm capacitance. We observed that the capacitance of the biofilm increased from 2 μF cm−2 to 450 μF cm−2 during biofilm growth, showing a relationship with current and total produced charge. These results suggest that biofilm capacitance is a measure for the amount of active biomass in bioelectrochemical systems. At the end of the experiment, the biofilm was harvested from the FTO electrode and an average yield of 0.55 g COD biomass/mol e− was determined.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Research group: Bio- and Circular Economy, Wageningen University and Research Centre, Wetsus, Centre for Sustainable Water Technology, Universitat Jaume I

The influence of epoxy resin modification by 3-aminopropyltriethoxysilane (APTES) on various properties of warp knitted viscose fabric is reported in this study. Dynamic mechanical, impact resistance, flexural, thermal properties, and burning behavior of the epoxy/viscose fabric composites are studied with respect to varying content of silane coupling agent. The results obtained for APTES-modified epoxy resin based composites reinforced with unmodified viscose fabric composites are compared to unmodified epoxy resin based composites reinforced with APTES-modified viscose fabric. The dynamic mechanical behavior of the APTES-modified resin based composites indicates improved interfacial adhesion. The composites prepared from modified epoxy resin exhibited a twofold increase in impact resistance. The improved adhesion between the fiber and modified resin was also visible from the scanning electron microscope analysis of the impact fracture surface. There was less influence of resin modification on the flexural properties of the composites. The 5% APTES modification induced early degradation of composites compared to all other composites. The burning rate of all the composites under study is rated to be satisfactory for use in automotive interior applications.

Source-separated urine is a promising stream for nutrient capture using electrochemical technologies. It contains the majority of macronutrients present in municipal wastewater in a concentrated, high ionic conductivity liquid and in N:P:K ratios suitable for agricultural application. The purpose of this study was to recover nutrients from urine, and particularly nitrogen as a solid without any chemical addition. Simulated source-separated urine was concentrated using a three-compartment electrochemical system, applying a range of current densities and feed compositions. Electro-concentration into a liquid concentrate reached maximum recovery of 72:61:79% for N:P:K, respectively, from a synthetic feed simulating ureolysed and digested urine, with a specific electrical energy consumption of 47 MJ/kg N and current efficiency of 67% for ammonium. Cooling the concentrate to −18 °C resulted in solid ammonium bicarbonate crystal formation in samples with high ammonium bicarbonate ionic product and high relative ammonium bicarbonate ionic strength. Precipitation started to occur when ammonium bicarbonate ionic product was higher than 2.25 M2 and ammonium bicarbonate accounted for more than 62% of the total ionic strength of the feed. The maximum observed nitrogen recovery into solid ammonium bicarbonate reached 17% using a current density of 100 A m−2. Based on these results, electro-concentration is a promising technology for urine nutrient capture. However, capture as solid ammonium bicarbonate is feasible only if higher recovery efficiencies are achieved by removing competing ions.

A compact olfactometer for IMS measurements and testing human perception

Production of easily controllable and measurable odor stimuli is needed when studying human olfaction, olfaction-related physiology and psychological reactions to odors. Controlled odor producing instruments are called olfactometers. For testing and calibrating new olfactometers or sensor arrays, a reliable input signal has to be produced to verify their accurate functionality. A common input signal in various olfactometers has been the use of volatile organic compounds (VOCs) in gaseous form. We present a compact olfactometer able to produce controlled continuous odor stimuli from three individual channels. For measuring the output gas flow, we used a ChemPro 100i (Environics, Finland) device that is based on aspiration ion mobility spectrometry (aIMS). IMS is a robust and sensitive method for measuring VOCs and is used especially in detecting toxic industrial chemicals and chemical warfare agents, but the technology is also suitable for other olfactory-related applications. The olfactometer was used to produce synthetic jasmine scent using three main odor components from jasmine oil and all the components were diluted using propylene glycol. The dilutions were supplied to the system using programmable syringe pumps, which guided the dilutions to individual evaporation units. We conducted experiments to verify the functionality of our olfactometer. Analysis of the ChemPro100i data showed that olfactometer can use different odor components to produce continuous, stable output flows with controlled concentrations.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Faculty of Biomedical Sciences and Engineering, Research group: Micro and Nanosystems Research Group, Research group: Sensor Technology and Biomeasurements (STB)

Bibliographical note

Effects of pyrolysis temperature on the hydrologically relevant porosity of willow biochar

Biochar pore space consists of porosity of multiple length scales. In direct water holding applications like water storage for plant water uptake, the main interest is in micrometre-range porosity since these pores are able to store water that is easily available for plants. Gas adsorption measurements which are commonly used to characterize the physical pore structure of biochars are not able to quantify this pore-size range. While pyrogenetic porosity (i.e. pores formed during pyrolysis process) tends to increase with elevated process temperature, it is uncertain whether this change affects the pore space capable to store plant available water. In this study, we characterized biochar porosity with x-ray tomography which provides quantitative information on the micrometer-range porosity. We imaged willow dried at 60 °C and biochar samples pyrolysed in three different temperatures (peak temperatures 308, 384, 489 °C, heating rate 2 °C min−1). Samples were carefully prepared and traced through the experiments, which allowed investigation of porosity development in micrometre size range. Pore space was quantified with image analysis of x-ray tomography images and, in addition, nanoscale porosity was examined with helium ion microscopy. The image analysis results show that initial pore structure of the raw material determines the properties of micrometre-range porosity in the studied temperature range. Thus, considering the pore-size regime relevant to the storage of plant available water, pyrolysis temperature in the studied range does not provide means to optimize the biochar structure. However, these findings do not rule out that process temperature may affect the water retention properties of biochars by modifying the chemical properties of the pore surfaces.

In this article, interaction between ZnCdSeS quantum dot (QD) and phthalocyanines with variable linker has been reported. Steady-state and time-resolved spectroscopic investigation reveals that only photoinduced energy transfer occurs from QD to phthalocyanines. To evaluate quantitatively the energy transfer, the Poisson statistics of QD-dye complex formation was used in the analysis of steady-state and time-resolved emission quenching, which allows to estimate the energy transfer rate constant for an ideal one-to-one complex. The measured rate constants are compared to the rates evaluated based on the classic Förster theory, which shows roughly 1 nm discrepancy in the energy transfer distance estimation, or one order in magnitude discrepancy in the transfer rate constants.

Selenate removal in biofilm systems: Effect of nitrate and sulfate on selenium removal efficiency, biofilm structure and microbial community

BACKGROUND: Selenium (Se) discharged into natural waterbodies can accumulate over time and have negative impacts on the environment. Se-laden wastewater streams can be treated using biological processes. However, the presence of other electron acceptors in wastewater, such as nitrate (NO3-) and sulfate (SO42-), can influence selenate (SeO42-) reduction and impact the efficiency of biological treatment systems. RESULTS: SeO42- removal by biofilms formed from an anaerobic sludge inoculum was investigated in the presence of NO3- and SO42- using drip flow reactors operated continuously for 10days at pH7.0 and 30°C. The highest total Se (∼60%) and SeO42- (∼80%) removal efficiencies were observed when the artificial wastewater contained SO42-. A maximum amount of 68μmol Se cm-2 was recovered from the biofilm matrix in SO42-+SeO42- exposed biofilms and biofilm mass was 2.7-fold increased for biofilms grown in the presence of SO42-. When SeO42- was the only electron acceptor, biofilms were thin and compact. In the simultaneous presence of NO3- or SO42-, biofilms were thicker (> 0.6mm), less compact and exhibited gas pockets. CONCLUSION: The presence of SO42- had a beneficial effect on biofilm growth and the SeO42- removal efficiency, while the presence of NO3- did not have a significant effect on SeO42- removal by the biofilms.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Hydraulic and Environmental Engineering (IHE) Inst. for Water Education, Montana State University (MSU), Bhabha Atomic Research Centre, UPEM

Design aspects of all atomic layer deposited TiO2–Fe2O3 scaffold-absorber photoanodes for water splitting

Iron and titanium oxides have attracted substantial attention in photoelectrochemical water splitting applications. However, both materials suffer from intrinsic limitations that constrain the final device performance. In order to overcome the limitations of the two materials alone, their combination has been proposed as a solution to the problems. Here we report on the fabrication of an atomic layer deposited (ALD) Fe2O3 coating on porous ALD-TiO2. Our results show that successful implementation requires complete mixing of the TiO2 and Fe2O3 layers via annealing resulting in the formation of a photoactive iron titanium oxide on the surface. Moreover, we found that incomplete mixing leads to crystallization of Fe2O3 to hematite that is detrimental to the photoelectrochemical performance. IPCE and transient photocurrent measurements performed using UV and visible light excitation confirmed that the iron titanium oxide extends the photocurrent generation to the visible range. These measurements were complemented by transient absorption spectroscopy (TAS), which revealed a new band absent in pristine hematite or anatase TiO2 that we assign to charge transfer within the structure. Taken together, these results provide design guidelines to be considered when aiming to combine TiO2 and Fe2O3 for photoelectrochemical applications.

Printable piezoelectric sensors were fabricated on a flexible polyethylene terephthalate (PET) substrate. Solution-processed piezoelectric poly(vinylidenefluoride-co-trifluoroethylene) ink was used as an active layer. Evaporated silver on PET was used as the bottom electrode and the painted silver glue as the top electrode. The sensors were poled using a high dc electric field from 25 to 65 MV m-1, yielding piezoelectric normal direction sensitivities up to 25 pC N-1. Bending-mode sensitivities showed values up to 200 nC N-1, which is 4 orders of magnitude larger than the force sensitivity in the normal direction. The high bending-mode sensitivities suggest suitability for detecting small forces, such as single fiber bonds or cardiomyocyte cell-beating force.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Faculty of Biomedical Sciences and Engineering, Nokia Technologies, University of Twente

Purpose: Bioadhesion is an important property of biological membranes, that can be utilized in pharmaceutical and biomedical applications. In this study, we have fabricated mucoadhesive drug releasing films with bio-based, non-toxic and biodegradable polymers that do not require chemical modifications. Methods: Nanofibrillar cellulose and anionic type nanofibrillar cellulose were used as film forming materials with known mucoadhesive components mucin, pectin and chitosan as functional bioadhesion enhancers. Different polymer combinations were investigated to study the adhesiveness, solid state characteristics, film morphology, swelling, mechanical properties, drug release with the model compound metronidazole and in vitro cytotoxicity using TR146 cells to model buccal epithelium. Results: SEM revealed lamellar structures within the films, which had a thickness ranging 40–240 μm depending on the film polymer composition. All bioadhesive components were non-toxic and showed high adhesiveness. Rapid drug release was observed, as 60–80% of the total amount of metronidazole was released in 30 min depending on the film formulation. Conclusions: The liquid molding used was a straightforward and simple method to produce drug releasing highly mucoadhesive films, which could be utilized in treating local oral diseases, such as periodontitis. All materials used were natural biodegradable polymers from renewable sources, which are generally regarded as safe.

Effect of surfactant type and sonication energy on the electrical conductivity properties of nanocellulose-CNT nanocomposite films

We present a detailed study on the influence of sonication energy and surfactant type on the electrical conductivity of nanocellulose-carbon nanotube (NFC-CNT) nanocomposite films. The study was made using a minimum amount of processing steps, chemicals and materials, to optimize the conductivity properties of free-standing flexible nanocomposite films. In general, the NFC-CNT film preparation process is sensitive concerning the dispersing phase of CNTs into a solution with NFC. In our study, we used sonication to carry out the dispersing phase of processing in the presence of surfactant. In the final phase, the films were prepared from the dispersion using centrifugal cast molding. The solid films were analyzed regarding their electrical conductivity using a four-probe measuring technique. We also characterized how conductivity properties were enhanced when surfactant was removed from nanocomposite films; to our knowledge this has not been reported previously. The results of our study indicated that the optimization of the surfactant type clearly affected the formation of freestanding films. The effect of sonication energy was significant in terms of conductivity. Using a relatively low 16 wt. % concentration of multiwall carbon nanotubes we achieved the highest conductivity value of 8.4 S/cm for nanocellulose-CNT films ever published in the current literature. This was achieved by optimizing the surfactant type and sonication energy per dry mass. Additionally, to further increase the conductivity, we defined a preparation step to remove the used surfactant from the final nanocomposite structure.

Hetero atom doped graphene - metal nanoparticle hybrids have received increasing attention owing to their unique electronic properties, large specific surface area, very high conductivity and more electronic interactions. Herein, we report for the first time a hydrothermal assisted strategy for developing novel class of nitrogen (N) and sulfur (S) co-doped graphene/Ag nano morphotypes (sphere, cube and wire) hybrids for enhanced optical limiting (OL) and surface-enhanced Raman scattering (SERS) applications. Two probe molecules, Rhodamine 6G and para-aminothiophenol, are chosen to determine the enhancement performance of the as-prepared SERS-active substrate. Our results signified that the Ag nanocube-N, S codoped graphene hybrid based SERS-active substrate presents excellent performances for sensing R6G with an enhancement factor of 1.07 × 107. Further, this SERS substrate reveals outstanding capability to detect P-ATP molecules with detection limit of approximately 1.0 × 10−12 M. Moreover, the non-linear optical absorption studies results show that the OL properties were appreciably enhanced after the insertion of Ag nanostructures on the NSG surface. Thus, OL properties of the two-dimensional N, S-codoped graphene can be effectively modified by absorbing AgNPs of different morphology on its surface. All of the results signify that these hybrid structures will show extended applications for SERS sensing and optoelectronic fields.

Respiration rate (RR) provides useful information for assessing the status of a patient. We propose RR estimation based on photoplethysmography (PPG) because the blood perfusion dynamics are known to carry information on breathing, as respiration-induced modulations in the PPG signal. We studied the use of amplitude variability of transmittance mode finger PPG signal in RR estimation by comparing four time-frequency (TF) representation methods of the signal cascaded with a particle filter. The TF methods compared were short-time Fourier transform (STFT) and three types of synchrosqueezing methods. The public VORTAL database was used in this study. The results indicate that the advanced frequency reallocation methods based on synchrosqueezing approach may present improvement over linear methods, such as STFT. The best results were achieved using wavelet synchrosqueezing transform, having a mean absolute error and median error of 2.33 and 1.15 breaths per minute, respectively. Synchrosqueezing methods were generally more accurate than STFT on most of the subjects when particle filtering was applied. While TF analysis combined with particle filtering is a promising alternative for real-time estimation of RR, artefacts and non-respiration-related frequency components remain problematic and impose requirements for further studies in the areas of signal processing algorithms an PPG instrumentation.

Bibliographical note

Evaluation of dry electrodes in canine heart rate monitoring

The functionality of three dry electrocardiogram electrode constructions was evaluated by measuring canine heart rate during four different behaviors: Standing, sitting, lying and walking. The testing was repeated (n = 9) in each of the 36 scenarios with three dogs. Two of the electrodes were constructed with spring-loaded test pins while the third electrode was a molded polymer electrode with Ag/AgCl coating. During the measurement, a specifically designed harness was used to attach the electrodes to the dogs. The performance of the electrodes was evaluated and compared in terms of heartbeat detection coverage. The effect on the respective heart rate coverage was studied by computing the heart rate coverage from the measured electrocardiogram signal using a pattern-matching algorithm to extract the R-peaks and further the beat-to-beat heart rate. The results show that the overall coverage ratios regarding the electrodes varied between 45-95% in four different activity modes. The lowest coverage was for lying and walking and the highest was for standing and sitting.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Faculty of Biomedical Sciences and Engineering, Pervasive Computing, Research group: Sensor Technology and Biomeasurements (STB), University of Helsinki, Institute of Biomedical Engineering and Informatics, University of Tampere (UTA), Research Group for Emotions

Effect of Co-Adsorbate and Hole Transporting Layer on the Photoinduced Charge Separation at the TiO2-Phthalocyanine Interface

Understanding the primary processes of charge separation (CS) in solid-state dye-sensitized solar cells (DSSCs) and, in particular, analysis of the efficiency losses during these primary photoreactions is essential for designing new and efficient photosensitizers. Phthalocyanines (Pcs) are potentially interesting sensitizers having absorption in the red side of the optical spectrum and known to be efficient electron donors. However, the efficiencies of Pc-sensitized DSSCs are lower than that of the best DSSCs, which is commonly attributed to the aggregation tendency of Pcs. In this study, we employ ultrafast spectroscopy to discover why and how much does the aggregation affect the efficiency. The samples were prepared on a standard fluorine-doped tin oxide (FTO) substrates covered by a porous layer of TiO2 nanoparticles, functionalized by a Pc sensitizer and filled by a hole transporting material (Spiro-MeOTAD). The study demonstrates that the aggregation can be suppressed gradually by using co-adsorbates, such as chenodeoxycholic acid (CDCA) and oleic acid, but rather high concentrations of co-adsorbate is required. Gradually, a few times improvement of quantum efficiency was observed at sensitizer/co-adsorbate ratio Pc/CDCA = 1:10 and higher. The time-resolved spectroscopy studies were complemented by standard photocurrent measurements of the same sample structures, which also confirmed gradual increase in photon-to-current conversion efficiency on mixing Pc with CDCA.

Membrane proteins are functionally regulated by the composition of the surrounding lipid bilayer. The late endosomal compartment is a central site for the generation of ceramide, a bioactive sphingolipid, which regulates responses to cell stress. The molecular interactions between ceramide and late endosomal transmembrane proteins are unknown. Here, we uncover in atomistic detail the ceramide interaction of Lysosome Associated Protein Transmembrane 4B (LAPTM4B), implicated in ceramide-dependent cell death and autophagy, and its functional relevance in lysosomal nutrient signaling. The ceramide-mediated regulation of LAPTM4B depends on a sphingolipid interaction motif and an adjacent aspartate residue in the protein's third transmembrane (TM3) helix. The interaction motif provides the preferred contact points for ceramide while the neighboring membrane-embedded acidic residue confers flexibility that is subject to ceramide-induced conformational changes, reducing TM3 bending. This facilitates the interaction between LAPTM4B and the amino acid transporter heavy chain 4F2hc, thereby controlling mTORC signaling. These findings provide mechanistic insights into how transmembrane proteins sense and respond to ceramide.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, University of Helsinki Faculty of Medicine, Minerva Foundation Institute for Medical Research Helsinki, Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Laboratory of Physics, Abo Akademi University, Queens College, City University of New York, University of Helsinki

We have studied the etching of GaInNAs, GaInNAsSb, and GaNAsSb alloys by NH4OH, H2SO4, and H3PO4 based solutions. NH4OH based solutions resulted in smooth surface, while other solutions created rougher and granular surfaces. The etch rates were found to increase with the Sb content. For GaInNAs, x-ray photoelectron spectroscopy revealed the enrichment of In on the etched surfaces, indicating In or In oxides having a smaller removal rate compared to Ga or Ga oxides. The enrichment of In was associated with smoother surfaces after etching and an enhanced photoluminescence caused by lower surface recombination due to reduced surface state density.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Photonics, Research group: ORC, Department of Physics and Astronomy, University of Turku, Turun Yliopisto/Turun Biomateriaalikeskus

Bibliographical note

Free amino acids and 5′-nucleotides in Finnish forest mushrooms

Edible mushrooms are valued because of their umami taste and good nutritional values. Free amino acids, 5′-nucleotides and nucleosides were analyzed from four Nordic forest mushroom species (Lactarius camphoratus, Boletus edulis, Cantharellus cibarius, Craterellus tubaeformis) using high precision liquid chromatography analysis. To our knowledge, these taste components were studied for the first time from Craterellus tubaeformis and Lactarius camphoratus. The focus was on the umami amino acids and 5′-nucleotides. The free amino acid and 5′-nucleotide/nucleoside contents of studied species differed from each other. In all studied samples, umami amino acids were among five major free amino acids. The highest concentration of umami amino acids was on L. camphoratus whereas B. edulis had the highest content of sweet amino acids and C. cibarius had the highest content of bitter amino acids. The content of umami enhancing 5′-nucleotides were low in all studied species.

Characteristics of nFOG, an aerosol-based wet thin film coating technique

An atmospheric pressure aerosol-based wet thin film coating technique called the nFOG is characterized and applied in polymer film coatings. In the nFOG, a fog of droplets is formed by two air-assist atomizers oriented toward each other inside a deposition chamber. The droplets settle gravitationally and deposit on a substrate, forming a wet film. In this study, the continuous deposition mode of the nFOG is explored. We determined the size distribution of water droplets inside the chamber in a wide side range of 0.1–100 µm and on the substrate using aerosol measurement instruments and optical microscopy, respectively. The droplet size distribution was found to be bimodal with droplets of approximately 30–50 µm contributing the most to the mass of the formed wet film. The complementary measurement methods allow us to estimate the role of different droplet deposition mechanisms. The obtained results suggest that the deposition velocity of the droplets is lower than the calculated terminal settling velocity, likely due to the flow fields inside the chamber. Furthermore, the mass flux of the droplets onto the substrate is determined to be in the order of 1 g/m3s, corresponding to a wet film growth rate of 1 µm/s. Finally, the nFOG technique is demonstrated by preparing polymer films with thicknesses in the range of approximately 0.1–20 µm.

Bibliographical note

Accurate Binding of Sodium and Calcium to a POPC Bilayer by Effective Inclusion of Electronic Polarization

Binding affinities and stoichiometries of Na+ and Ca2+ ions to phospholipid bilayers are of paramount significance in the properties and functionality of cellular membranes. Current estimates of binding affinities and stoichiometries of cations are, however, inconsistent due to limitations in the available experimental and computational methods. In this work, we improve the description of the binding details of Na+ and Ca2+ ions to a 1-palmitoyl-2-oleoyl-phosphatidylcholine (POPC) bilayer by implicitly including electronic polarization as a mean field correction, known as the electronic continuum correction (ECC). This is applied by scaling the partial charges of a selected state-of-the-art POPC lipid model for molecular dynamics simulations. Our improved ECC-POPC model reproduces not only the experimentally measured structural parameters for the ion-free membrane, but also the response of lipid headgroup to a strongly bound cationic amphiphile, as well as the binding affinities of Na+ and Ca2+ ions. With our new model, we observe on the one side negligible binding of Na+ ions to POPC bilayer, while on the other side stronger interactions of Ca2+ primarily with phosphate oxygens, which is in agreement with the previous interpretations of the experimental spectroscopic data. The present model results in Ca2+ ions forming complexes with one to three POPC molecules with almost equal probabilities, suggesting more complex binding stoichiometries than those from simple models used to interpret the NMR data previously. The results of this work pave the way to quantitative molecular simulations with realistic electrostatic interactions of complex biochemical systems at cellular membranes.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, Research group: Biological Physics and Soft Matter, Research area: Computational Physics, Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Department of Physical Chemistry, University of Helsinki Institute of Biotechnology

Biopolymers are attractive candidates to fabricate biocompatible hydrogels, but the low water solubility of most of them at physiological pH has hindered their applications. To prepare a water-soluble derivative of chitosan (WSC) biopolymer, it was grafted with a small anionic amino acid, l-glutamic acid, using a single-step 1-ethyl-3-[3-dimethylaminopropyl]carbodiimide coupling reaction. This resulted in a zwitterion-tethered structure onto the polymer backbone. The degree of substitution range was 13–16 ± 1.25%, which was controlled by varying the feeding reagent ratios. Differential scanning calorimetry- and X-ray diffraction-based analysis confirmed a transition from amorphous into a moderately amorphous/crystalline morphology after amino acid grafting, which made the derivative water-soluble at physiological pH. Composite hydrogels gelated within 60 s when using this WSC together with benzaldehyde-terminated 4-arm poly(ethylene glycol) as cross-linker. The compressive modulus of these hydrogels could be easily tuned between 4.0 ± 1.0 and 31 ± 2.5 kPa, either by changing the cross-linker concentration or total solid content in the final gel. The gels were injectable at the lowest cross-linker as well as total solid content, due to the enhanced elastic behavior. These hydrogels showed biodegradability during a 1 month incubation period in phosphate-buffered saline with weight remaining of 60 ± 1.5 and 44 ± 1.45% at pHs 7.4 and 6.5, respectively. The cytocompatibility of the gels was tested using the fibroblast cell line (i.e., WI-38), which showed good cell viability on the gel surface. Therefore, these hydrogels could be an important injectable biomaterial for delivery purpose in the future.

Membrane bound COMT isoform is an interfacial enzyme: General mechanism and new drug design paradigm

The enzyme catechol-O-methyltransferase (COMT) has water soluble (S-COMT) and membrane associated (MB-COMT), bitopic, isoforms. Of these MB-COMT is a drug target in relation to the treatment of Parkinson's disease. Using a combination of computational and experimental protocols, we have determined the substrate selection mechanism specific to MB-COMT. We show: (1) substrates with preferred affinity for MB-COMT over S-COMT orient in the membrane in a fashion conducive to catalysis from the membrane surface and (2) binding of COMT to its cofactor ADOMET induces conformational change that drives the catalytic surface of the protein to the membrane surface, where the substrates and Mg2+ ions, required for catalysis, are found. Bioinformatics analysis reveals evidence of this mechanism in other proteins, including several existing drug targets. The development of new COMT inhibitors with preferential affinity for MB-COMT over S-COMT is now possible and insight of broader relevance, into the function of bitopic enzymes, is provided.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Universite de Geneve

Properties of HVOF-sprayed Stellite-6 coatings

Stellite-6 coatings were deposited onto AISI 304 stainless steel substrate by gas-fueled HVOF spraying, systematically varying the process parameter settings. By operating the HVOF torch with a fuel-rich mixture, dense coatings (<1% porosity) are produced, containing up to ≈3 vol% oxide inclusions. A substantial amount of a Cr-rich f.c.c. phase is found, mainly produced by quenching of molten lamellae, and distinct from the equilibrium, Co-based f.c.c. solid solution retained in unmelted particles. These coatings exhibit pseudo-passive behavior and survive 5 cycles (100 h) of the Corrodkote test (ASTM B380-97) with no substrate corrosion. Coatings obtained from oxygen-rich mixtures, on the other hand, contain fewer oxide inclusions but also greater porosity, and do not protect the substrate against corrosion. The wear behavior of the coatings is less influenced by deposition conditions. In ball-on-disk dry sliding tests, all coatings exhibit wear rates of 2–3 × 10−5 mm3/(N·m), higher than those reported for bulk or clad Stellite, because of interlamellar delamination. Strain-induced, “martensitic” phase transformation from the f.c.c. structure to a h.c.p. one is observed over a 1–2 μm depth below the contact surface. Additional tribo-oxidation is onset when frictional heat dissipation has heated the wear debris enough to trigger its reaction with the environment. Correspondingly, a transition to a regime of higher friction occurs (from ≈0.6 to ≈0.8). At 400 °C, lamellar delamination is suppressed but wear rates rise to 5–8 × 10−5 mm3/(N·m) because of abrasive and adhesive wear. At 800 °C, a dense “glaze” tribofilm is formed by sintered debris particles, firmly bonded to a thermally grown oxide scale on the underlying metal surface. The “glaze” protects the coating, lowering the wear rate to ≈1 × 10−5 mm3/(N·m) and the friction coefficient to <0.45. Under high-stress particle abrasion conditions, wear rates of ≈1 × 10−3 mm3/(N·m) are found.

Thermal Isomerization of Hydroxyazobenzenes as a Platform for Vapor Sensing

Photoisomerization of azobenzene derivatives is a versatile tool for devising light-responsive materials for a broad range of applications in photonics, robotics, microfabrication, and biomaterials science. Some applications rely on fast isomerization kinetics, while for others, bistable azobenzenes are preferred. However, solid-state materials where the isomerization kinetics depends on the environmental conditions have been largely overlooked. Herein, an approach to utilize the environmental sensitivity of isomerization kinetics is developed. It is demonstrated that thin polymer films containing hydroxyazobenzenes offer a conceptually novel platform for sensing hydrogen-bonding vapors in the environment. The concept is based on accelerating the thermal cis-trans isomerization rate through hydrogen-bond-catalyzed changes in the thermal isomerization pathway, which allows for devising a relative humidity sensor with high sensitivity and quick response to relative humidity changes. The approach is also applicable for detecting other hydrogen-bonding vapors such as methanol and ethanol. Employing isomerization kinetics of azobenzenes for vapor sensing opens new intriguing possibilities for using azobenzene molecules in the future.

Two experimental agglomerated and sintered (a&s) feedstock powders were prepared, in order to reveal the role of WC addition on the microstructure, hardness, and the abrasion resistance of HVOF-sprayed Cr3C2-NiCr coatings. These powders contained 10 wt.% of sub-micron WC, 20 or 10 wt.% of nickel binder, and Cr3C2 as balance. Experimental coatings were deposited by a liquid fueled high velocity oxygen-fuel (HVOF) spray process and subsequently heat treated at 800 °C for 8 h to simulate elevated temperature service conditions. The microstructures of the powders and coatings were studied by SEM and X-ray diffraction, and the hardnesses of coatings were probed by means of micro and nanoindentation. In addition, the high stress abrasion resistance was tested in a temperature range from room temperature up to 800 °C. The microstructural characterization of the coatings displayed the presence of WC and tungsten containing Cr3C2 grains. The coating hardness increased after heat treatment, which stemmed from precipitation of secondary carbides and solid solution strengthening of the binder by tungsten. In addition, the study revealed that both experimental coatings have high wear resistance at room and elevated temperatures.

Regenerative medicine, especially cell therapy combined with a supportive biomaterial scaffold, is considered to be a potential treatment for various deficits in humans. Here, we have produced and investigated the detailed properties of injectable hydrazone crosslinked hyaluronan-polyvinyl alcohol (HA-PVA) and alginate-polyvinyl alcohol (AL-PVA) hydrogels to be used as a supportive biomaterial for 3D neural cell cultures. To the best of our knowledge, this is the first time the polymerization and properties of hydrazone crosslinked AL-PVA hydrogel have been reported. The effect of the degree of substitution and molecular weight of the polymer components as well as the polymer concentration of the hydrogel on the swelling, degradation and mechanical properties of the hydrogels is reported. Furthermore, we studied the effect of the above parameters on the growth of human pluripotent stem cell-derived neuronal cells. The most neural cell supportive HA-PVA hydrogel was composed of high molecular weight HA component with brain-mimicking mechanical properties and decreased polymer concentration. AL-PVA hydrogel, with stiffness quite similar to brain tissue, was also shown to be similarly supportive. Neuronal spreading and 3D network formation was enhanced inside the softest hydrogels.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Faculty of Biomedical Sciences and Engineering, Research group: Biomaterials and Tissue Engineering Group, BioMediTech Institute and Faculty of Medicine and Life Sciences

Amorphous titanium dioxide (a-TiO2) combined with an electrocatalyst has shown to be a promising coating for stabilizing traditional semiconductor materials used in artificial photosynthesis for efficient photoelectrochemical solar-to-fuel energy conversion. In this study we report a detailed analysis of two methods of modifying an undoped thin film of atomic layer deposited (ALD) a-TiO2 without an electrocatalyst to affect its performance in water splitting reaction as a protective photoelectrode coating. The methods are high-temperature annealing in ultrahigh vacuum and atomic hydrogen exposure. A key feature in both methods is that they preserve the amorphous structure of the film. Special attention is paid to the changes in the molecular and electronic structure of a-TiO2 induced by these treatments. On the basis of the photoelectrochemical results, the a-TiO2 is susceptible to photocorrosion but significant improvement in stability is achieved after heat treatment in vacuum at temperatures above 500 °C. On the other hand, the hydrogen treatment does not increase the stability despite the ostensibly similar reduction of a-TiO2. The surface analysis allows us to interpret the improved stability to the thermally induced formation of O- species within a-TiO2 that are essentially electronic defects in the anionic framework.

An activity recognition framework deploying the random forest classifier and a single optical heart rate monitoring and triaxial accelerometer wrist-band

Wrist-worn sensors have better compliance for activity monitoring compared to hip, waist, ankle or chest positions. However, wrist-worn activity monitoring is challenging due to the wide degree of freedom for the hand movements, as well as similarity of hand movements in different activities such as varying intensities of cycling. To strengthen the ability of wrist-worn sensors in detecting human activities more accurately, motion signals can be complemented by physiological signals such as optical heart rate (HR) based on photoplethysmography. In this paper, an activity monitoring framework using an optical HR sensor and a triaxial wrist-worn accelerometer is presented. We investigated a range of daily life activities including sitting, standing, household activities and stationary cycling with two intensities. A random forest (RF) classifier was exploited to detect these activities based on the wrist motions and optical HR. The highest overall accuracy of 89.6 ± 3.9% was achieved with a forest of a size of 64 trees and 13-s signal segments with 90% overlap. Removing the HR-derived features decreased the classification accuracy of high-intensity cycling by almost 7%, but did not affect the classification accuracies of other activities. A feature reduction utilizing the feature importance scores of RF was also carried out and resulted in a shrunken feature set of only 21 features. The overall accuracy of the classification utilizing the shrunken feature set was 89.4 ± 4.2%, which is almost equivalent to the above-mentioned peak overall accuracy.

A furan-based synthetic biopolymer composed of a bifuran monomer and ethylene glycol was synthesized through melt polycondensation, and the resulting polyester was found to have promising thermal and mechanical properties. The bifuran monomer, dimethyl 2,2′-bifuran-5,5′-dicarboxylate, was prepared using a palladium-catalyzed, phosphine ligand-free direct coupling protocol. A titanium-catalyzed polycondensation procedure was found effective at polymerizing the bifuran monomer with ethylene glycol. The prepared bifuran polyester exhibited several intriguing properties including high tensile modulus. In addition, the bifuran monomer furnished the polyester with a relatively high glass transition temperature. Films prepared from the new polyester also had excellent oxygen and water barrier properties, which were found to be superior to those of poly(ethylene terephthalate). Moreover, the novel polyester also has good ultraviolet radiation blocking properties.

The autoxidative condensation of 2-aryl-2-lithio-1,3-dithianes is here reported. Treatment of 2-aryl-1,3-dithianes with n-BuLi in the absence of any electrophile leads to condensation of three molecules of 1,3-dithianes and formation of highly functionalized α-thioether ketones orthothioesters in 51-89% yields upon air exposure. The method was further expanded to benzaldehyde dithioacetals, affording corresponding orthothioesters and α-thioether ketones in 48-97% yields. The experimental results combined with density functional theory studies support a mechanism triggered by the autoxidation of 2-aryl-2-lithio-1,3-dithianes to yield a highly reactive thioester that undergoes condensation with two other molecules of 2-aryl-2-lithio-1,3-dithiane.

A sol-gel transformation of liquid silica precursor to solid silica particles was carried out in a one-pot synthesis way, where a solution of styrene butadiene elastomer was present. The composites, thus produced, offered remarkable improvements of mechanical and dynamic mechanical performances compared to precipitated silica. The morphological analysis reveals that the alkoxy-based silica particles resemble a raspberry structure when the synthesis of the silica was carried out in the presence of polymer molecules and represent a much more open silica-network structure. However, in the absence of the polymer, the morphology of the silica particles is found to be different. It is envisaged that the special morphology of the in situ synthesized silica particles contributes to the superior reinforcement effects, which are associated with a strong silica-rubber interaction by rubber chains trapped inside the raspberry-like silica aggregates. Therefore, the interfaces are characterized in detail by low-field solid-state 1H NMR spectroscopy, 29Si solid-state NMR spectroscopy, and energy-dispersive X-ray spectroscopy. Low-field 1H NMR-based double-quantum experiments provide a quantitative information about the cross-link density of the silica-filled rubber composites and about the influence of silane coupling agent on the chemical cross-link density of the network and correlates well with equilibrium swelling measurements. The special microstructure of the alkoxy-based silica was found to be associated with the interaction between alkoxy-based silica and rubber chains as a consequence of particle growth in the presence of rubber chains.

MetrIntSimil-an accurate and robust metric for comparison of similarity in intelligence of any number of cooperative multiagent systems

Intelligent cooperative multiagent systems are applied for solving a large range of real-life problems, including in domains like biology and healthcare. There are very few metrics able to make an effective smeasure of the machine intelligence quotient. The most important drawbacks of the designed metrics presented in the scientific literature consist in the limitation in universality, accuracy, and robustness. In this paper, we propose a novel universal metric called MetrIntSimil capable of making an accurate and robust symmetric comparison of the similarity in intelligence of any number of cooperative multiagent systems specialized in difficult problem solving. The universality is an important necessary property based on the large variety of designed intelligent systems. MetrIntSimil makes a comparison by taking into consideration the variability in intelligence in the problem solving of the compared cooperativemultiagent systems. It allows a classification of the cooperativemultiagent systems based on their similarity in intelligence. A cooperative multiagent system has variability in the problem solving intelligence, and it can manifest lower or higher intelligence in different problem solving tasks. More cooperative multiagent systems with similar intelligence can be included in the same class. For the evaluation of the proposed metric, we conducted a case study for more intelligent cooperative multiagent systems composed of simple computing agents applied for solving the Symmetric Travelling Salesman Problem (STSP) that is a class of NP-hard problems. STSP is the problem of finding the shortest Hamiltonian cycle/tour in a weighted undirected graph that does not have loops or multiple edges. The distance between two cities is the same in each opposite direction. Two classes of similar intelligence denoted IntClassA and IntClassB were identified. The experimental results show that the agent belonging to IntClassA intelligence class is less intelligent than the agents that belong to the IntClassB intelligence class.

High purity porous ZnO nanopyramids with controllable properties are grown on their tips on Si(100) substrates by means of a catalyst-free vapor phase deposition route in a wet oxygen reaction environment. The system degree of preferential [001] orientation, as well as nanopyramid size, geometrical shape, and density distribution, can be finely tuned by varying the growth temperature between 300 and 400 °C, whereas higher temperatures lead to more compact systems with a three-dimensional (3D) morphology. A growth mechanism of the obtained ZnO nanostructures based on a self-catalytic vapor-solid (VS) mode is proposed, in order to explain the evolution of nanostructure morphologies as a function of the adopted process conditions. The results obtained by a thorough chemico-physical characterization enable us to get an improved control over the properties of ZnO nanopyramids grown by this technique. Taken together, they are of noticeable importance not only for fundamental research on ZnO nanomaterials with controlled nano-organization but also to tailor ZnO functionalities in view of various potential applications.

In this work, we report about the mechanical relaxation characteristics of an intrinsically self-healable imidazole modified commercial rubber. This kind of self-healing rubber was prepared by melt mixing of 1-butyl imidazole with bromo-butyl rubber (bromine modified isoprene-isobutylene copolymer, BIIR). By this melt mixing process, the reactive allylic bromine of bromo-butyl rubber was converted into imidazole bromide salt. The resulting development of an ionic character to the polymer backbone leads to an ionic association of the groups which ultimately results to the formation of a network structure of the rubber chains. The modified BIIR thus behaves like a robust crosslinked rubber and shows unusual self-healing properties. The non-covalent reversible network has been studied in detail with respect to stress relaxation experiments, scanning electron microscopic and X-ray scattering.

Photophysical control and switching on organic-inorganic hybrid interfaces are of great interest in diverse fundamental and applicative research areas. 6,13-Bis(triisopropylsilylethynyl)pentacene (TP) is well-known to exhibit efficient singlet fission (SF) for generation of high-yield triplet excited states in aggregated forms, whereas perylenediimide (PDI) ensembles show the characteristic excimer formation. Additionally, a combination of pentacene (electron donor: D) and PDI (electron acceptor: A) is expected to undergo an efficient photoinduced electron transfer (PET), and absorption of two chromophores combined covers the entire visible region. Therefore, the concentration-dependent mixed self-assembled monolayers (SAMs) composed of two chromophores enable us to control and switch the photophysical processes on a surface. In this work, a series of mixed SAMs composed of TP and PDI units on gold nanoclusters (GNCs) were newly synthesized by changing the relative molecular concentration ratios. Structural control of mixed SAMs on a gold surface based on the concentration ratios was successfully achieved. Time-resolved femtosecond and nanosecond transient absorption measurements clearly demonstrate photophysical control and switching of the above competitive reactions such as SF, electron transfer (ET) and excimer formation. The maximum quantum yields of triplet states (ΦT = ∼170%) and electron transfer (ΦET = ∼95%) were quantitatively evaluated by changing the concentration ratios. The rate constants of SF and excimer processes are largely dependent on the concentration ratios, whereas the rate constants of ET processes approximately remain constant. These findings are also discussed based on the statistical framework of the assembly of chromophores on the gold surface.

The direct doping method was applied to fabricate upconverter fluorophosphate glasses in the system (90NaPO3-(10-x)Na2O-xNaF) (mol%) by adding NaYF4:Er3+,Yb3+ nanocrystals. An increase in the network connectivity, a red shift of the optical band gap and a decrease in the thermal properties occur when Na2O is progressively replaced by NaF. To ensure the survival and the dispersion of the nanocrystals in the glasses with x = 0 and 10, three doping temperatures (Tdoping) (525, 550 and 575 °C) at which the nanocrystals were added in the glass melt after melting and 2 dwell times (3 and 5 minutes) before quenching the glasses were tested. Using 5 wt% of the NaYF4:Er3+,Yb3+ nanocrystals, green emission from the NaYF4:Er3+,Yb3+ nanocrystals-containing glasses was observed using a 980 nm pumping, the intensity of which depends on the glass composition and on the direct doping parameters (Tdoping and dwell time). The strongest upconversion was obtained from the glass with x = 10 prepared using a Tdoping of 550 °C and a 3 min dwell time. Finally, we showed that the upconversion, the emission at 1.5 μm and of the transmittance spectra of the nanocrystals-containing glasses could be measured to verify if decomposition of the nanocrystals occurred in glass melts during the preparation of the glasses.

Photoresponsive liquid crystals (LCs) whose alignment can be controlled with UV-Visible light are appealing for a range of photonic applications. From the perspective of exploring the interplay between the light response and the self-assembly of the molecular components, supramolecular liquid crystals are of particular interest. They allow elaborating the structure-property relationships that govern the optical performance of LC materials by subtle variation of the chemical structures of the building blocks. Herein we present a supramolecular system comprising azophenols and stilbazoles as hydrogen-bond donors and acceptors, respectively, and show that ortho-fluorination of the azophenol dramatically increases the thermal stability of the LC phases, an important characteristics in their further utilization in photonics. The systems exhibit fast photoinduced order-disorder transitions, and rapid recovery of the liquid-crystalline state once the light irradiation is ceased, due to the photochemical properties of azophenols.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Research group: Chemistry & Advanced Materials, University of Duisburg-Essen

Improved electromechanical response in acrylic rubber by different carbon-based fillers

Dielectric elastomers are materials often utilized for the fabrication of electroactive actuators. Acrylic rubber (ACM) is very widely used in dielectric elastomer actuators (DEAs). However, its overall good performance is limited by the high operating electric field required. In the present work, we compare the effect of different types of conventionally used carbon black (CB) as well as other carbon-based fillers on the dielectric and actuation properties of ACM in order to show that performance of DEAs can be improved by the development of ACM composites. Indeed, addition of CB, carbon nanotubes (CNTs), and synthetic graphite leads to an increase in the relative dielectric permittivity of elastomeric material. Moreover, incorporation of nanodiamonds results in reduction of dielectric losses. Finally, actuation stress is remarkably improved by CNTs and different grades of CB.

The modification of epoxy resin by 3-aminopropyltriethoxysilane (APTES) to improve the tensile properties of warp knitted viscose fabric composites is reported in this study. The study evaluates the efficiency of modification methods adopted to modify the epoxy resin and the influence of the resin modification on various properties of the cured castings. The influence of matrix resin modification on the tensile properties of viscose fabric composite is compared to those prepared from chemically modified fibre. The efficiency of the modification was determined through titration method to determine the epoxide content of epoxy resin, viscosity measurement and FTIR. The effect of APTES modification on various properties of cured castings is studied through differential scanning calorimeter, contact angle measurement and tensile testing. The addition of APTES into the epoxy resin decreased the epoxide content in the resin as evident from the titration method. The tensile strength of cured castings decreased after the resin modification. The tensile strength and elongation at break of the viscose fabric composites prepared from modified resin, increased up to 14 and 41%, respectively. The improved adhesion of APTES-modified epoxy resin to the viscose fibre is confirmed from SEM analysis of tensile fracture surface.

Bibliographical note

Adsorption of furfural from torrefaction condensate using torrefied biomass

Torrefaction is a biomass energy densification process that generates a major byproduct in the form of torrefaction condensate. Microbial conversion of torrefaction condensate could be an attractive option for energy integration within torrefaction process. However, torrefaction condensate contains several compounds, such as furfural, 5-hydroxymethylfurfural and guaiacol that are inhibitory to microbes. In this study, for the first time, we reported detoxification of torrefaction condensate, by removing the major inhibitory compound furfural, using torrefied biomass and later used the detoxified torrefaction condensate for anaerobic digestion. The effect of varying torrefaction temperature (225–300 °C), torrefied biomass dosage (25–250 g/L), initial pH (2.0–9.0), and contact time (1–12 h) on furfural adsorption was studied with batch adsorption experiments. The furfural adsorption on torrefied biomass was best represented by pseudo second order kinetic model. The adsorption of furfural and other inhibitory compounds on torrefied biomass was likely a hydrophobic interaction. A maximum of 60% of furfural was adsorbed from torrefaction condensate containing 9000 mg furfural/L using 250 g/L of torrefied biomass in batch adsorption. For, column (20 mm internal diameter and 200 mm bed height), the saturation time for furfural adsorption was around 50 min. Anaerobic digestion of the detoxified torrefaction condensate shows that the lag phase in methane production was reduced from 25 d to 15 d for 0.2 volatile solid (VS)substrate:VSinoculum loading. The study shows that torrefaction condensate can be effectively detoxified using torrefied biomass for microbial conversion and can be integrated within the torrefied biomass pellet production process.

Sulfur deactivation and regeneration behavior of the Pd/Al2O3 catalyst has been investigated via experimental characterization and density functional theory (DFT) simulations. During the sulfur exposure, PdO crystallites grow slightly while bulk Al2(SO4)3 forms on the support. DFT calculations indicate that SOx species interact strongly with the catalyst surface making it chemically inactive in agreement with the experimental results. During the regeneration treatment (CH4 conditions), PdO particles reduce, Al2(SO4)3 is partially removed, and the activity for CH4 conversion is increased. No full recovery can be observed due to remaining Al2(SO4)3, the formation of encapsulating sulfur species, and the partial reduction of PdO particles. To reoxidize Pd, the catalyst is further regenerated (O2 conditions). The resulting CH4 conversion is at the same level than with the regenerated catalyst. Thus, a small amount of Al2(SO4)3 appears to have a stronger effect on the performance than the state of Pd.

Composition and role of the attached and planktonic microbial communities in mesophilic and thermophilic xylose-fed microbial fuel cells

A mesophilic (37 °C) and a thermophilic (55 °C) two-chamber microbial fuel cell (MFC) were studied and compared for their power production from xylose and the microbial communities involved. The anode-Attached, membrane-Attached, and planktonic microbial communities, and their respective active subpopulations, were determined by next generation sequencing (Illumina MiSeq), based on the presence and expression of the 16S rRNA gene. Geobacteraceae accounted for 65% of the anode-Attached active microbial community in the mesophilic MFC, and were associated to electricity generation likely through direct electron transfer, resulting in the highest power production of 1.1 W m-3. A lower maximum power was generated in the thermophilic MFC (0.2 W m-3), likely due to limited acetate oxidation and the competition for electrons by hydrogen oxidizing bacteria and hydrogenotrophic methanogenic archaea. Aerobic microorganisms, detected among the membrane-Attached active community in both the mesophilic and thermophilic MFC, likely acted as a barrier for oxygen flowing from the cathodic chamber through the membrane, favoring the strictly anaerobic exoelectrogenic microorganisms, but competing with them for xylose and its degradation products. This study provides novel information on the active microbial communities populating the anodic chamber of mesophilic and thermophilic xylose-fed MFCs, which may help in developing strategies to favor exoelectrogenic microorganisms at the expenses of competing microorganisms.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Research group: Bio- and Circular Economy, Natl. University of Ireland, Galway, Institute for Water Education, Hydraulic and Environmental Engineering (IHE) Inst. for Water Education

Findings on the decomposition of persistent luminescent (PeL) SrAl2O4:Eu2+,Dy3+ microparticles (MPs) in phosphate glass melt under static condition are reported. PeL phosphate glasses with the composition (50P2O5-10Na2O-40SrO) (in mol%) were prepared by adding the MPs in the glass melt. The decomposition of the MPs occurs during the preparation of the glass and leads to changes in the Eu2+ sites and to the formation of Eu3+ which decreases the PeL properties of the glasses. The decomposition of the MPs depends on the temperature at which the MPs are added in the melt and also on the time before casting the melts.

Gloriosa superba Mediated Synthesis of Platinum and Palladium Nanoparticles for Induction of Apoptosis in Breast Cancer

Green chemistry approaches for designing therapeutically significant nanomedicine have gained considerable attention in the past decade. Herein, we report for the first time on anticancer potential of phytogenic platinum nanoparticles (PtNPs) and palladium nanoparticles (PdNPs) using a medicinal plant Gloriosa superba tuber extract (GSTE). The synthesis of the nanoparticles was completed within 5 hours at 100°C which was confirmed by development of dark brown and black colour for PtNPs and PdNPs, respectively, along with enhancement of the peak intensity in the UV-visible spectra. High-resolution transmission electron microscopy (HRTEM) showed that the monodispersed spherical nanoparticles were within a size range below 10 nm. Energy dispersive spectra (EDS) confirmed the elemental composition, while dynamic light scattering (DLS) helped to evaluate the hydrodynamic size of the particles. Anticancer activity against MCF-7 (human breast adenocarcinoma) cell lines was evaluated using MTT assay, flow cytometry, and confocal microscopy. PtNPs and PdNPs showed 49.65 ± 1.99% and 36.26 ± 0.91% of anticancer activity. Induction of apoptosis was most predominant in the underlying mechanism which was rationalized by externalization of phosphatidyl serine and membrane blebbing. These findings support the efficiency of phytogenic fabrication of nanoscale platinum and palladium drugs for management and therapy against breast cancer.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Faculty of Biomedical Sciences and Engineering, Modern College of Arts, Savitribai Phule Pune University, Indian Institute of Science, Bangalore, Department of Biomedical Sciences and Engineering, Defense Institute of Advanced Technology, Indian Institute of Technology Bombay, RK University

Ultraviolet radiation (UV-R) causes genotoxic and aging effects on skin, and sunscreens are used to alleviate the damage. However, sunscreens contain synthetic shielding agents that can cause harmful effects in the environment. Nature-derived substances may have potential as replacement materials for the harmful sunscreen chemicals. However, screening of a broad range of samples is tedious, and often requires a separate genotoxicity assessment. We describe a simple microplate technique for the screening of UV protective substances using a recombinant Escherichia coli biosensor. Both absorbance-based and bioactivity-based shields can be detected with simultaneous information about the sample genotoxicity. With this technique, a controversial sunscreen compound, oxybenzone offers physical or absorbance-based shield but appears genotoxic at higher concentrations (3.3 mg/mL). We also demonstrate that pine needle extract (PiNe) shields the biosensor from UV-R in a dose-dependent manner without showing genotoxicity. The physical shield of 5 mg/mL PiNe was similar to that of one of the most common UV-shielding compound TiO2 concentration 0.80 mg/mL. The bioactivity-based shield of PiNe also reaches the extent of the physical shield with the highest concentration (3.3 mg/mL). We conclude that our technique is suitable in detecting the UV-shielding potential of natural substances, and gives simultaneous information on genotoxicity.

Bibliographical note

Detection and characterization at nM concentration of oligomers formed by hIAPP, Aβ(1-40) and their equimolar mixture using SERS and MD simulations

We report a structural investigation on IAPP, Aβ(1-40) and their equi-molar mixture aggregation pathway at nano-molar concentration using the Surface Enhanced Raman Spectroscopy (SERS) effect induced by silver metal colloids prepared by laser processes in solution and molecular dynamics simulations. Our data show the ability of silver NPs coupled with SERS to detect secondary structures of IAPP, Aβ(1-40) and their 1:1 molar ratio mixture in the oligomeric state. The preparation of silver colloids shows superior performance with respect to chemically prepared nano-particles. SERS spectroscopy shows both selectivity and sensitivity in detecting the secondary structures of hIAPP and Aβ(1-40) and to recognize both proteins in their mixture. On the other hand, molecular dynamics simulations confirm SERS structural data and the given atomistic details about the structural organization of IAPP and Aβ(1-40) oligomers. Our study shows an inhomogeneity in the chemical composition of IAPP/Aβ(1-40) oligomer aggregates.

We studied natural and forestry-drained peatlands to examine the effect of over 34 years lowered water table on the δ13C values of vegetation, bulk peat and subsoil. In the seven studied sites, δ13C in the basal peat layer was 1.1 and 1.2 ‰ lower than that of the middle-layer and surface layer, respectively. Furthermore, there was a positive correlation between the δ13C values of the basal and surface peat layers, possibly due to carbon (C) recycling within the peat column. In the same mire complex, natural fen peat δ13C values were lower than those of the nearby bog, possibly due to the dominance of vascular plants on fen and the generally larger share of recycled C in the fens than in the bogs. Furthermore, natural and 51 years previously drained fen and bog, on the opposite sides of a ditch on the same mire complex, showed no significant differences in δ13C values. Plant δ13C values were lower, while δ13C values of subsoil were higher in the drained than in the natural site of the fen.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Chemistry and Bioengineering, Research group: Bio- and Circular Economy, University of Eastern Finland, University of Jyväskylä

Optical frequency comb photoacoustic spectroscopy

We report the first photoacoustic detection scheme using an optical frequency comb - optical frequency comb photoacoustic spectroscopy (OFC-PAS). OFC-PAS combines the broad spectral coverage and the high resolution of OFCs with the small sample volume of cantilever-enhanced PA detection. In OFC-PAS, a Fourier transform spectrometer (FTS) is used to modulate the intensity of the exciting comb source at a frequency determined by its scanning speed. One of the FTS outputs is directed to the PA cell and the other is measured simultaneously with a photodiode and used to normalize the PA signal. The cantilever-enhanced PA detector operates in a non-resonant mode, enabling detection of a broadband frequency response. The broadband and the high-resolution capabilities of OFC-PAS are demonstrated by measuring the rovibrational spectra of the fundamental C-H stretch band of CH4, with no instrumental line shape distortions, at total pressures of 1000 mbar, 650 mbar, and 400 mbar. In this first demonstration, a spectral resolution two orders of magnitude better than previously reported with broadband PAS is obtained, limited by the pressure broadening. A limit of detection of 0.8 ppm of methane in N2 is accomplished in a single interferogram measurement (200 s measurement time, 1000 MHz spectral resolution, 1000 mbar total pressure) for an exciting power spectral density of 42 μW/cm-1. A normalized noise equivalent absorption of 8 × 10-10 W cm-1 Hz-1/2 is obtained, which is only a factor of three higher than the best reported with PAS based on continuous wave lasers. A wide dynamic range of up to four orders of magnitude and a very good linearity (limited by the Beer-Lambert law) over two orders of magnitude are realized. OFC-PAS extends the capability of optical sensors for multispecies trace gas analysis in small sample volumes with high resolution and selectivity.

On the molecular optical nonlinearity of halogen-bond-forming azobenzenes

We study hyper-Rayleigh scattering and computed molecular hyperpolarizability in a series of azobenzene chromophores in chloroform and dimethylformamide as solvents. The chromophores form halogen or hydrogen bonds of varying strength with dimethylformamide molecules, differently from what is expected for chloroform. We show that hyperpolarizability is unaffected or sligthly lower with the azobenzene forming the strongest halogen bond. Solid supramolecular polymers with the same chromophores have previously demonstrated clearly higher second-order nonlinear responses when a halogen-bond-accepting polymer is used, the larger increase being associated with the stronger halogen bond. The present study proves that the higher optical nonlinearity in polymers lies in the better ordering of the chromophores instead of changes in molecular hyperpolarizability, highlighting the unique properties of halogen bonding in supramolecular chemistry.

Structural dynamics of the polyethylenimine-DNA and poly(l-lysine)-DNA complexes (polyplexes) was studied by steady-state and time-resolved fluorescence spectroscopy using the fluorescence resonance energy transfer (FRET) technique. During the formation of the DNA polyplexes, the negative phosphate groups (P) of DNA are bound by the positive amine groups (N) of the polymer. At N/P ratio 2, nearly all of the DNA's P groups are bound by the polymer N groups: These complexes form the core of the polyplexes. The excess polymer, added to this system to increase the N/P ratio to the values giving efficient gene delivery, forms a positively charged shell around the core polyplex. We investigated whether the exchange between the core and shell regions of PEI and PLL polyplexes takes place. Our results demonstrated a clear difference between the two studied polymers. Shell PEI can replace PEIs previously attached to DNA in the polyplex core, while PLL cannot. Such a dynamic structure of PEI polyplexes compared to a more static one found for PLL polyplexes partially explains the observed difference in the DNA transfection efficiency of these polyplexes. Moreover, the time-resolved fluorescence spectroscopy revealed additional details on the structure of PLL polyplexes: In between the core and shell, there is an intermediate layer where both core and shell PLLs or their parts overlap.

Droplets slip and bounce on superhydrophobic surfaces, enabling remarkable functions in biology and technology. These surfaces often contain microscopic irregularities in surface texture and chemical composition, which may affect or even govern macroscopic wetting phenomena. However, effective ways to quantify and map microscopic variations of wettability are still missing, because existing contact angle and force-based methods lack sensitivity and spatial resolution. Here, we introduce wetting maps that visualize local variations in wetting through droplet adhesion forces, which correlate with wettability. We develop scanning droplet adhesion microscopy, a technique to obtain wetting maps with spatial resolution down to 10 μm and three orders of magnitude better force sensitivity than current tensiometers. The microscope allows characterization of challenging non-flat surfaces, like the butterfly wing, previously difficult to characterize by contact angle method due to obscured view. Furthermore, the technique reveals wetting heterogeneity of micropillared model surfaces previously assumed to be uniform.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Faculty of Biomedical Sciences and Engineering, Research group: Micro and Nanosystems Research Group, Research group: Bioinspired Materials and Robotics (BMR), Aalto University, Helsinki University of Technology

Creating efficient water-borne dispersions based mainly on renewable materials for coating of flexible packaging paper was the aim of this study. The effects of an ethylene modified poly(vinyl alcohol) grade and a standard poly(vinyl alcohol) on the oxygen and water vapor barrier performance of corn starch and potato starch coatings was studied. The results showed that a coating composition with a high fraction of a renewable polymer was effective in keeping the oxygen barrier at a technically and commercially applicable level. An ethylene modified poly(vinyl alcohol) grade was found to provide lower oxygen transmission rates at high relative humidity, as compared to a standard poly(vinyl alcohol) grade. The oxygen barrier properties of blends of starch and poly(vinyl alcohol) were similar to that of the pure modified poly(vinyl alcohol) in the range from 0% starch to 60% starch. This was observed with both hydroxypropylated and octenyl succinate modified starch grades. The drying conditions of the mixed starch:poly(vinyl alcohol) coatings were based on drying trials with pure poly(vinyl alcohol) coatings. Drying at moderate temperatures indicated the possibility to slightly decrease water vapor transmission rate by higher drying temperature. Several secondary effects of increased drying temperature such as coating hold-out and formation of defects may also be of importance.

Efficient synthetic methods for carbazole-based small molecule electron donors with donor–acceptor (D–A) and A–D–A type structures were developed. In order to study the relation between chemical structures and material properties, the prepared compounds were characterized in detail using absorption spectroscopy, differential pulse voltammetry, and computational methods. In addition, symmetrical A–D–A type compounds were tested as an active layer component in bulk heterojunction based organic solar cell (OSC) devices with conventional structure. The results show that the two compound types have many similar properties. However, the extended molecular structure of A–D–A type compounds offer better film forming properties and higher molar absorption coefficients compared with the D–A type materials. Furthermore, the attachment of fluoro substituents in the A units has a positive effect on all solar cell device parameters. Moreover, the computational studies revealed that the molecular structures are twisted between the central carbazole D unit and π-bridge which may result in inefficient intramolecular charge transfer and, also, relatively limited short-circuit currents in OSC devices.

DoGlycans-Tools for Preparing Carbohydrate Structures for Atomistic Simulations of Glycoproteins, Glycolipids, and Carbohydrate Polymers for GROMACS

Carbohydrates constitute a structurally and functionally diverse group of biological molecules and macromolecules. In cells they are involved in, e.g., energy storage, signaling, and cell-cell recognition. All of these phenomena take place in atomistic scales, thus atomistic simulation would be the method of choice to explore how carbohydrates function. However, the progress in the field is limited by the lack of appropriate tools for preparing carbohydrate structures and related topology files for the simulation models. Here we present tools that fill this gap. Applications where the tools discussed in this paper are particularly useful include, among others, the preparation of structures for glycolipids, nanocellulose, and glycans linked to glycoproteins. The molecular structures and simulation files generated by the tools are compatible with GROMACS.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, Research group: Biological Physics and Soft Matter, University of Helsinki, Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, MEMPHYS - Centre for Biomembrane Physics, University of Southern Denmark, Laboratory of Physics

Starch and poly(vinyl alcohol) based barrier coatings for flexible packaging papers were studied. Both octenyl succinate modified and hydroxypropylated corn and potato starches were blended with regular and ethylene modified poly(vinyl alcohol) to increase the water vapor barrier properties and enhance the flexibility of the starch coatings, in order to accomplish superior barrier performance. Phase separation between starch and poly(vinyl alcohol) was studied in detail, both in the solution and in dry draw-down coatings on paper. The barrier performance of the coated paper was evaluated with respect to water vapor transmission rate. Conditions for the creation of a thin surface layer consisting of only one of the pure polymers were identified and discussed in terms of phase separation in solution migration of poly(vinyl alcohol) to the uppermost surface layer. The phase separation promoted low water vapor transmission rates also with a rather high fraction of starch in the coatings.

Systematic analysis of coating-substrate interactions in the presence of flow localization

Localized deformation and cracking in a system of thermally sprayed hard metal coating overlaid on a low alloy steel is studied by means of bend testing. In-situ digital image correlation measurements are used to characterize material strain field near the coating/substrate interface. The studied substrate undergoes softening upon yielding which manifests itself as narrow bands of localized shear deformation. The measurements show that the coating cracks and the substrate shear bands interact. When the coating starts cracking during the elastic loading of the substrate, the formed cracks function as nucleation points for the shear bands. In contrast, if the coating resists cracking until the yielding of the substrate, the coating cracks and substrate shear bands form simultaneously. Based on the experiments, continuum-scale finite element model of the system is developed, validated and then used for a systematic numerical analysis of the effects of substrate shear banding on the measurement of coating properties. Based on the results of this work, three main effects can be identified. Firstly, the flow localization in the substrate can increase the measured apparent (macroscopic) surface strain of the coating, if not accounted for by using microscopic techniques. Secondly, substrate shear bands increase the interfacial loading, which may cause unexpected delamination of the coating and thus affect the evaluation of the interfacial strength. Finally, substrate shear bands affect the stress state within the coating and may thus affect the cracking morphology in the coating. Therefore, based on the results of this study, if the coating and interfacial strengths are of similar magnitude with the substrate yield strength, the possible tendency of the substrate towards flow localization should be taken into account in the analysis of the coating behavior.

Membrane Binding of Recoverin: From Mechanistic Understanding to Biological Functionality

Recoverin is a neuronal calcium sensor involved in vision adaptation that reversibly associates with cellular membranes via its calcium-activated myristoyl switch. While experimental evidence shows that the myristoyl group significantly enhances membrane affinity of this protein, molecular details of the binding process are still under debate. Here, we present results of extensive molecular dynamics simulations of recoverin in the proximity of a phospholipid bilayer. We capture multiple events of spontaneous membrane insertion of the myristoyl moiety and confirm its critical role in the membrane binding. Moreover, we observe that the binding strongly depends on the conformation of the N-terminal domain. We propose that a suitable conformation of the N-terminal domain can be stabilized by the disordered C-terminal segment or by binding of the target enzyme, i.e., rhodopsin kinase. Finally, we find that the presence of negatively charged lipids in the bilayer stabilizes a physiologically functional orientation of the membrane-bound recoverin.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Institute of Experimental Botany of the Academy of Sciences of the Czech Republic, University of Stuttgart, University of Helsinki

Exhaust emissions emitted by a non-road mobile machine were studied chasing a tractor in real-world conditions and repeating the same transient tests with a similar engine on an engine dynamometer where additionally, non-road steady state tests were carried out. The engines were equipped with an oxidation catalyst (DOC) and a selective catalytic reduction (SCR) system, and they were fuelled by fossil diesel fuel with ultra-low sulphur content and hydrotreated vegetable oil (HVO). By substituting diesel fuel with HVO the on-road emissions of nitrogen oxides (NOx) reduced 20% and particle number 44%, the emission factors being EFNOx = 1.62 ± 0.04 g/kWh and EFN = (28.2 ± 7.8) × 1013 #/kWh. Similar trend was observed for NOx at laboratory although the emissions were somewhat smaller than on-road. In contrast to real-world, in the laboratory experiment the EFN was only 2% smaller with HVO than with diesel, and these emission factors were almost one order of magnitude smaller than observed on-road. The number size distribution and volatility measurements showed that in real-world experiments small nucleation mode particles were formed during uphill and during downhill in engine braking conditions. These were not observed at laboratory. However, nucleation mode particles were observed in the laboratory experiments at high load steady driving conditions. At steady state tests the emissions strongly depended on engine load and engine speed with both fuels.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Physics, Research area: Aerosol Physics, University of Helsinki, Turku University of Applied Sciences

Feed-hopper level estimation and control in cone crushers

This paper describes a novel feed-hopper level estimation and control scheme for addressing the known problem of unreliable and occasionally corrupted feed-hopper level measurement in a cone crusher. The approach involves estimating the feed-hopper level with an adaptive time-variant state estimator. The proposed adaptive scheme delivers asymptotically unbiased feed-hopper level estimates, despite using an inherently biased state estimator with biased measurement(s) and/or model, and therefore addresses the common pitfall of state estimators. The paper details the entire control system design procedure, from the fundamental theory, through dynamic modeling and estimator/controller tuning, to the design validation and control performance evaluation. The performance of the proposed scheme is evaluated through extensive full-scale tests in various production scenarios, including process start-up, level setpoint changes, and mass flow disturbance rejection. The full-scale tests revealed a number of benefits compared to the straightforward level control implementation. These benefits include the possibility of recovering from a temporary loss of measurement signal, smaller control effort, and increased system robustness due to an increased ability to withstand measurement errors. Therefore, the proposed scheme will enable more consistent size reduction and provide protection against performance degradation and process down-time.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Automation and Hydraulic Engineering, Chalmers University of Technology

Configurational Disorder of Water Hydrogen-Bond Network at the Protein Dynamical Transition

We introduce a novel strategy to quantify the disorder of extended water-water hydrogen-bond (HB) networks sampled in particle-based computer simulations. The method relies on the conformational clustering of the HB connectivity states. We successfully applied it to unveil the fine relationship among the protein dynamical transition in hydrated powder, which marks the activation of protein flexibility at Td ≈ 240 K, and the sudden increase in the configurational disorder of the water HB network enveloping the proteins. Our finding links, in the spirit of the Adam-Gibbs relationship, the diffusivity of protein atoms, as quantified by the hydrogen mean-square displacements, and the thermodynamic solvent configurational entropy.

Vegetable fillers for electric stimuli responsive elastomers

Dielectric elastomer actuators (DEAs) have been studied widely in recent years for artificial muscle applications, but their implementation into production is limited due to high operating voltages required. The actuation behavior of dielectric elastomer under an applied electric field is predicted by Maxwell's pressure and thickness strain equations. According to these equations, the best electromechanical response is achieved when the relative permittivity is high and elastic modulus is low. The potential source for additives increasing the relative permittivity of rubbers can be vegetable powders that have much higher dielectric constant than common elastomers. In the present research, the dielectric and actuation properties of polyacrylate rubber (ACM) were studied after the addition of different vegetable-based fillers such as potato starch, corn starch, garlic, and paprika. The results were compared to ACM filled with barium titanate. The compounds containing vegetable fillers showed higher relative dielectric permittivity at 1 Hz frequency than the compounds containing barium titanate due to higher interfacial polarization. The actuation studies showed that lower electric fields are required to generate certain actuation forces when the starches and garlic are used in the rubber instead of barium titanate. Therefore, the vegetable-based fillers can be used to improve actuation performance of DEAs.

We report the capacitive behavior of electrochemically polymerized polyazulene films in different ionic liquids. The ionic liquids in this study represent conventional imidazolium based ionic liquids with tetrafluoroborate and bis(trifluoromethylsulfonyl)imide anions as well as an unconventional choline based ionic liquid. The effect of different ionic liquids on the polymerization and capacitive performance of polyazulene films is demonstrated by cyclic voltammetry and electrochemical impedance spectroscopy in a 3-electrode cell configuration. The films exhibit the highest capacitances in the lowest viscosity ionic liquid (92 mF cm−2), while synthesis in high viscosity ionic liquid shortens the conjugation length and results in lower electroactivity (25 mF cm−2). The obtained films also show good cycling stabilities retaining over 90% of their initial capacitance over 1200 p-doping cycles. We also demonstrate, for the first time, flexible polyazulene supercapacitors of symmetric and asymmetric configurations using the choline based ionic liquid as electrolyte. In asymmetric configuration, capacitance of 55 mF (27 mF cm−2) with an equivalent series resistance of 19 Ω is obtained at operating voltage of 1.5 V. Upon increasing the operating voltage up to 2.4 V, the capacitance increases to 72 mF (36 mF cm−2).

The control of Simulated Moving Bed (SMB) units is challenging due to their complex dynamic behaviour and the difficulty of measuring their main properties. Furthermore, for the SMB units, the transfer function identification when the unit is operating at its optimal point is not easy to be done through the usual way. This work presents the development of a novel strategy to identify transfer functions of TMB/SMB and its application on classical linear model predictive controllers (MPC). However, for the process in study, due its unique dynamics, only the identification of the linear model is not enough to solve its control problem. Therefore, it is proposed a modification in the MPC prediction, that consists in a strategy based on a switching system where the most adequate transfer function is employed in the controller to overcome the problems related with the process dynamic behaviour. The results show that the used methodology enables the easy identification of transfer functions at the process optimal operating point and that the MPC can control the process in both the servo and regulator problem cases. It is also showed that the transfer function identified can be applied in the control of a SMB unit with four columns, under its optimal conditions.

We report herein unprecedented long-range observation of both formation and decay of the exciplex state in donor (D)-bridge (B)-acceptor (A) linked systems. Zinc porphyrins (ZnP) as a donor were tethered to single-walled carbon nanotube (SWNT) as an acceptor through oligo(p-phenylene)s (ZnP-phn-SWNT) or oligo(p-xylene)s (ZnP-xyn-1-ph1-SWNT) with systematically varied lengths (n = 1-5) to address the issue. Exponential dependencies of rate constants for the exciplex formation (kFEX) and decay (kDEX) on the edge-to-edge separation distance between ZnP and SWNT through the bridges were unambiguously derived from time-resolved spectroscopies. Distance dependencies (i.e., attenuation factor, β) of kFEX and kDEX in ZnP-phn-SWNT were found to be considerably small (β = 0.10 for kFEX and 0.12 Å-1 for kDEX) compared to those for charge separation and recombination (0.2-0.8 Å-1) in D-B-A systems with the same oligo(p-phenylene) bridges. The small β values may be associated with the exciplex state with mixed characters of charge-transfer and excited states. In parallel, the substantially nonconjugated bridge of oligo(p-xylene)s exhibited larger attenuation values (β = 0.12 for kFEX and 0.14 Å-1 for kDEX). These results provide deep insight into the unique photodynamics of electronically strongly coupled D-B-A systems involving exciplex.

Comparison of starch and gelatin hydrogels for non-toxic supercapacitor electrolytes

Starch and gelatin are two of the most abundantly available natural polymers. Their non-toxicity, low cost, and compatibility with aqueous solvents make them ideal for use in ubiquitous, environmentally friendly electronics systems. This work presents the results of conductivity measurements through impedance spectroscopy for gelatin- and starch-based aqueous gel electrolytes. The NaCl-based gels were physically cross-linked. The conductivity values were 84.6 mS/cm at 1.5 mol L−1 and 71.5 mS/cm at 2 mol L−1 for gelatin and starch, respectively. The mechanical properties of gelatin were found preferable to those of starch, although they deteriorated significantly when the salt concentration exceeded 2 mol L−1. The ability of the gels to successfully act as a supercapacitor electrolyte was demonstrated with printed electrodes on plastic substrate. The devices were characterized through cyclic voltammetry measurements. The results imply that these polymer gel electrolytes are very promising for replacing the traditional aqueous liquid electrolytes in supercapacitors in applications where, for example, user and environmental safety is essential.

Density functional simulations have been performed for Au7Cu23 and Au23Cu7 clusters on MgO(100) supports to probe their catalytic activity for CO oxidation. The adsorption of reactants, O2 and CO, and potential O2 dissociation have been investigated in detail by tuning the location of vacancies (F-center, V-center) in MgO(100). The total charge on Au7Cu23 and Au23Cu7 is negative on all supports, regardless of the presence of vacancies, but the effect is significantly amplified on the F-center. Au7Cu23/MgO(100) and Au23Cu7/MgO(100) with an F-center are the only systems to bind O2 more strongly than CO. In each case, O2 can be effectively activated upon adsorption and dissociated to 2 × O atoms. The different reaction paths based on the Langmuir-Hinshelwood (LH) and Eley-Rideal (ER) mechanisms for CO oxidation have been explored on the Au7Cu23 and Au23Cu7 clusters on F-centers, and the results are compared with the previous findings for Au15Cu15. Overall, the reaction barriers are small, but the changes in the Au:Cu ratio tune the reactant adsorption energies and sites considerably, showing also varying selectivity for CO and O2. The microkinetic model built on the basis of the above results shows a pronounced CO2 production rate at low temperature for the clusters on F-centers.

Geometric Structure and Chemical Ordering of Large AuCu Clusters: A Computational Study

Understanding the structure and composition of nanosized gold-copper (AuCu) clusters is crucial for designing an effective AuCu catalyst. Global optimization of AuCu clusters using atomistic force fields is a viable solution for clusters with at least a few nm sizes, because of its fast computation. Here we develop an atomistic many-body potential for AuCu on the basis of the second-moment approximation to the tight-binding model. We show that our potential is in good agreement with density-functional theory calculations, and use it to study the structure and chemical ordering of clusters of sizes up to ∼4 nm by means of global optimization searches. We show that the clusters present a surface enrichment in Au, while subsurface and central sites are enriched in Cu. Surface enrichment in Au and center enrichment in Cu are stronger in icosahedra. Surface Cu atoms prefer terrace sites on (111) facets. Both atomistic and DFT calculations show that L10 and L12 ordered phases are not favorable, even at their ideal compositions for these sizes, because of the tendency of Au to surface segregation. The stability range of icosahedral structures is wider in AuCu nanoalloys than in Au and Cu pure clusters.

Nematicon-enhanced spontaneous symmetry breaking

We investigate topological and optical spontaneous symmetry breaking in nematic liquid crystals subject to the Fréedericksz transition. Specular nematicon states couple to mirrored distributions of the director due to symmetry breaking, with transverse velocities controlled by beam power in the strong nonlinear regime. Hysteresis in transverse velocity versus incidence angle is observed in the soliton regime.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Photonics, University “Roma Tre”, University of Southampton, United Kingdom, Centro S3, Nonlinear Optics and OptoElectronics Lab, Optics Laboratory, Department of Physics, Tampere University of Technology

Density functional study of structure and dynamics in liquid antimony and Sbn clusters

Density functional/molecular dynamics simulations have been performed on liquid antimony (588 atoms and six temperatures between 600 K and 1300 K) and on neutral Sb clusters with up to 14 atoms. We study structural patterns (coordination numbers, bond angles, and ring patterns, structure factors, pair distribution functions) and dynamical properties (vibration frequencies, diffusion constants, power spectra, dynamical structure factors, viscosity) and compare with available experimental results and with the results of our previous simulations on Bi. Three short covalent bonds characteristic of pnictogens are common in the clusters, and higher temperatures lead in the liquid to broader bond angle distributions, larger total cavity volumes, and weaker correlations between neighboring bond lengths. There are clear similarities between the properties of Sb and Bi aggregates.

The effects of calcium and potassium on CO2 gasification of birch wood in a fluidized bed

Birch wood was leached of its naturally occurring ash forming elements and doped with three concentrations of calcium or potassium before being gasified in a laboratory bubbling fluidized bed reactor. The wood samples were pelletized and inserted into a fluidized bed reactor where they were first pyrolyzed with N2 and then gasified with CO2. In addition to tracking the gas concentration of the exit gas, char samples were taken from the fluidized bed and analyzed to study the char properties. The presence of potassium in the biomass was found to have a significant influence on the structure of the resulting char, however potassium did not have an observable catalytic effect on the overall gasification reaction rate with CO2 due to the formation of a unreactive coke layer on the char surface. In contrast, calcium did increase the char conversion rate and is likely the primary active catalyst in gasification of birch wood with CO2.

Phthalocyanines (Pc) are well-known light-harvesting compounds. However, despite the tremendous efforts on phthalocyanine synthesis, the achieved energy conversion efficiencies for Pc-based dye-sensitized solar cells are moderate. To cast light on the factors reducing the conversion efficiency, we have undertaken a time-resolved spectroscopy study of the primary photoinduced reactions at a semiconductor-Pc interface. ZnO nanorods were chosen as a model semiconductor substrate with enhanced specific surface area. The use of a nanostructured oxide surface allows to extend the semiconductor-dye interface with a hole transporting layer (spiro-MeOTAD) in a controlled way, making the studied system closer to a solid-state dye-sensitized solar cell. Four zinc phthalocyanines are compared in this study. The compounds are equipped with bulky peripheral groups designed to reduce the self-aggregation of the Pcs. Almost no signs of aggregation can be observed from the absorption spectra of the Pcs assembled on a ZnO surface. Nevertheless, the time-resolved spectroscopy indicates that there are inter-Pc charge separation-recombination processes in the time frame of 1-100 ps. This may reduce the electron injection efficiency into the ZnO by more than 50%, pointing out to a remaining aggregation effect. Surprisingly, the electron injection time does not correlate with the length of the linker connecting the Pc to ZnO. A correlation between the electron injection time and the "bulkiness" of the peripheral groups was observed. This correlation is further discussed with the use of computational modeling of the Pc arrangements on the ZnO surface. (Figure Presented).

Structural changes of PtPd nanoparticles in a natural gas oxidation catalyst were studied at elevated temperatures in air and low-oxygen conditions and in situ using environmental transmission electron microscopy (ETEM). The fresh catalyst shows x particles on the γ-Al2O3 support. At 700 °C, the noble metal oxide decomposes and Pt gets trapped by PdO particles followed by formation of metallic Pd and Pt containing particles. At 1000 °C, the particles had a metallic Pd and Pt containing core surrounded by PdO particles. In addition, the presence of

Purpose: To investigate the effect of compression on the crystallization behavior in amorphous tablets using sum frequency generation (SFG) microscopy imaging and more established analytical methods. Method: Tablets containing neat amorphous griseofulvin with/without excipients (silica, hydroxypropyl methylcellulose acetate succinate (HPMCAS), microcrystalline cellulose (MCC) and polyethylene glycol (PEG)) were prepared. They were analyzed upon preparation and storage using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM) and SFG microscopy. Results: Compression-induced crystallization occurred predominantly on the surface of the neat amorphous griseofulvin tablets, with minimal crystallinity being detected in the core of the tablets. The presence of various types of excipients was not able to mitigate the compression-induced surface crystallization of the amorphous griseofulvin tablets. However, the excipients affected the crystallization rate of amorphous griseofulvin in the core of the tablet upon compression and storage. Conclusions: SFG microscopy can be used in combination with ATR-FTIR spectroscopy and SEM to understand the crystallization behaviour of amorphous tablets upon compression and storage. When selecting excipients for amorphous formulations, it is important to consider the effect of the excipients on the physical stability of the amorphous formulations.

General information

Publication status: Published

MoE publication type: A1 Journal article-refereed

Organisations: Department of Chemistry and Bioengineering, University of Helsinki, Division of Biopharmaceutical Sciences, Biomedicum Imaging Unit, FIN-00014 University of Helsinki